Allergen reducing agent, and processed product, coating material, and wood building material using same

Abstract

An allergen reducing agent is provided that contains a terpenoid polymer or copolymer as an active component, and that functions to reduce allergens such as mites and pollen, and is capable of suppressing coloring.

Claims

1. A method for reducing an allergen comprising imparting an allergen reducing function to a surface of a target where allergens need to be suppressed by applying an allergen reducing agent containing, as an active component to the surface of the target, at least one of: a terpenoid-phenol copolymer having a structure represented by: ##STR00006## wherein m and n are positive intergers; or a terpenoid-phenol copolymer having a structure represented by: ##STR00007## wherein m and n are positive intergers.

2. The method for reducing an allergen according to claim 1, wherein the terpenoid-phenol copolymer has a hydroxyl number of 10 to 250 mgKOH/g.

3. The method for reducing an allergen according to claim 1, wherein a coating material containing the allergen reducing agent and a curable resin is applied to the surface of the target and cured.

4. The method for reducing an allergen according to claim 1, wherein the surface of the target is a surface of a wood base.

5. The method for reducing an allergen according to claim 1, wherein the allergen reducing agent contains the terpenoid-phenol copolymer having the structure represented by: ##STR00008##

6. The method for reducing an allergen according to claim 1, wherein the allergen reducing agent contains the hydrogenated terpenoid-phenol copolymer having the structure represented by: ##STR00009##

7. The method for reducing an allergen according to claim 1, wherein the allergen reducing agent contains the terpenoid-phenol copolymer having the structure represented by: ##STR00010## and contains the hydrogenated terpenoid-phenol copolymer having the structure represented by: ##STR00011##

Description

EXAMPLES

Example 1

(1) A terpene resin (YS resin 1250; Yasuhara Chemical; a compound having the structure of the formula (2) in the skeleton; 30 weight parts) was dissolved in a thinner (xylene:toluene=1:1; 60 weight parts) to produce an allergen reducing agent solution.

Example 2

(2) An allergen reducing agent solution was produced in the same manner as in Example 1, except that an aromatic modified terpene resin (YS resin TO125; Yasuhara Chemical; a compound having the structure of the formula (3) in the skeleton, where R is a hydrogen atom) was used instead of the terpen resin YS resin 1250.

Example 3

(3) A terpene phenolic resin (YS Polyster T130; Yasuhara Chemical; a compound having the structure of the formula (4) in the skeleton, where m=1; hydroxyl number of 60 mgKOH/g; 30 weight parts) was dissolved in a thinner (butyl acetate:ethyl acetate:methyl ethyl ketone=1:1:1; 60 weight parts) to produce an allergen reducing agent solution.

Example 4

(4) An allergen reducing agent solution was produced in the same manner as in Example 3, except that a terpene phenolic resin (Mighty Ace K145; Yasuhara Chemical; a compound having the structure of the formula (4) in the skeleton, where m=3; hydroxyl number of 200 mgKOH/g) was used instead of the terpene phenolic resin YS Polyster T130 used in Example 3.

Example 5

(5) An allergen reducing agent solution was produced in the same manner as in Example 3, except that a hydrogenated terpene phenolic resin (YS Polyster TH130; Yasuhara Chemical; a compound having the structure of the formula (6) in the skeleton, where m=1; hydroxyl number of 60 mgKOH/g) was used instead of the terpene phenolic resin YS Polyster T130 used in Example 3.

Comparative Example 1

(6) An allergen reducing agent solution was produced in the same manner as in Example 1, except that a polyvinyl phenolic resin (Maruka Lyncur M; Maruzen Petrochemical; a compound having the structure of the following formula (7) in the skeleton; where n is a positive integer) was used instead of the terpene resin YS resin 1250 used in Example 1.

(7) ##STR00005##

(8) The allergen reducing agent solutions obtained in Examples 1 to 5 and Comparative Example 1 were measured for hue and allergen reducing performance (percentage allergen reduction). The results are presented in Table 1.

(9) <Hue Measurement>

(10) The hue of the allergen reducing agent solution was measured by using the Gardner method. Evaluations were performed in the scale of 0 to 18. (0: colorless transparent; the color turns more brownish as the number increases).

(11) <Measurement of Allergen Reducing Performance>

(12) 1) Preparation of Allergen Solution

(13) An allergen solution was produced by dissolving an allergen freeze dried powder (purified mite antigen; Der2; Asahi Breweries Ltd.) in a phosphate buffer (pH7.6) so as to provide an allergen protein amount of 100 ng/ml.

(14) 2) Sample Preparation

(15) The allergen reducing agent solution was applied to a PET film with a bar coater #20, and dried at 80° C. for 30 min.

(16) 3) Reaction

(17) The allergen solution prepared in procedure 1) was dropped onto each film produced in procedure 2) and onto an unprocessed PET film in 400 μl portions, and the allergen protein amount was measured with an ELISA kit (Indoor) after 6 hours of reaction. The percentage allergen reduction was calculated as follows.
Percentage allergen reduction (%)=100×(1−A/B)

(18) A: allergen protein amount (ng/ml) on the film obtained in procedure 2) as measured after 6 hours

(19) B: allergen protein amount (ng/ml) on the unprocessed PET film as measured after 6 hours

(20) TABLE-US-00001 TABLE 1 Hue Percentage allergen (Gardner method) reduction (%) Ex. 1 3 87.8 Ex. 2 1 or less 89.9 Ex. 3 4.5 90.8 Ex. 4 4.5 79.5 Ex. 5 1 or less 85.1 Com. Ex. 1 17 75.6

(21) It was confirmed from the results presented in Table 1 that the allergen reducing agent solutions obtained in Examples 1 to 5 had less coloring than the allergen reducing agent solution obtained in Comparative Example 1. It was also confirmed that the processed products obtained by applying the allergen reducing agent solutions of Examples 1 to 5 had excellent allergen reducing performance, as did the processed product obtained by applying the allergen reducing agent solution of Comparative Example 1 containing a conventional allergen reducing agent.

Example 6

(22) A light-curable coating material was obtained by adding and stirring a terpene phenolic resin (YS Polyster T130; Yasuhara Chemical; 10 weight parts), urethane acrylate (product name: Shikou 7550B; Nippon Synthetic Chemical Industry Co., Ltd.; 30 weight parts), trimethylolpropane triacrylate (EO addition; product name: M310; Toagosei Co., Ltd.; 16 weight parts), tripropylene glycol (product name: M220; Toagosei Co., Ltd.; 18 weight parts), 1,9-nonanediol diacrylate (product name: L-9CA; Dai-Ichi Kogyo Seiyaku Co., Ltd.; 18 weight parts), methoxyglycol acrylate (product name: ME-3; Dai-Ichi Kogyo Seiyaku Co., Ltd.; 18 weight parts), hydrophobic silica (product name: Sylophobic 702; Fuji Silysia Chemical Ltd.; 5 weight parts), acrylic beads (product name: GM0401S; Ganz Chemical Co., Ltd.; 5 weight parts), and a photopolymerization initiator (product name: MBF; Ciba; 5 weight parts).

Example 7

(23) A light-curable coating material was obtained in the same manner as in Example 6, except that a terpene phenolic resin (Mighty Ace K145; Yasuhara Chemical) was used instead of the terpene phenolic resin YS Polyster T130 used in Example 6.

Example 8

(24) A light-curable coating material was obtained in the same manner as in Example 6, except that the hydrogenated terpene phenolic resin YS Polyster TH130 was used instead of the terpene phenolic resin YS Polyster T130 used in Example 6.

Comparative Example 2

(25) A light-curable coating material was obtained in the same manner as in Example 6, except that the polyvinylphenolic resin Maruka Lyncur M (Maruzen Petrochemical) was used instead of the terpene phenolic resin YS Polyster T130 used in Example 6.

Comparative Example 3

(26) A light-curable coating material was obtained in the same manner as in Example 6, except that the terpene phenolic resin YS Polyster T130 used in Example 6 was not mixed.

(27) The light-curable coating materials obtained in Examples 6 to 8 and Comparative Examples 2 and 3 were each applied to a white olefin sheet subjected beforehand to a pre-coating process with a bar coater #10, and cured by ultraviolet irradiation (illuminance of 350 to 400 mj/cm) to obtain a processed sheet.

(28) The processed sheets were measured for hue (coloring property), allergen reducing performance (percentage allergen reduction), heat resistance (resistance to discoloration under heat), lightfastness (resistance to discoloration under light), and chemical resistance. The results are presented in Table 2.

(29) <Hue (Coloring Property) Measurement>

(30) The processed sheets were measured for color difference ΔE with a color-difference meter. Evaluations were made according to the following criteria.

(31) ΔE≦1: Excellent

(32) 1<ΔE<2: Good

(33) ΔE≧2: Poor

(34) <Measurement of Allergen Reducing Performance>

(35) 1) Preparation of Allergen Solution

(36) An allergen solution was produced by dissolving an allergen freeze dried powder (purified mite antigen; Der2; Asahi Breweries Ltd.) in a phosphate buffer (pH 7.6) so as to provide an allergen protein amount of 20 ng/ml.

(37) 2) Reaction

(38) The allergen solution prepared in procedure 1) was dropped onto the processed sheets in 400 μl portions, and the allergen protein amount was measured with an ELISA kit (Indoor) after 6 hours of reaction. The percentage allergen reduction was calculated as follows.
Percentage allergen reduction (%)=100×(1−A/B)

(39) A: allergen protein amount (ng/ml) on the processed sheet using the light-curable coating materials of Examples 6 to 8 and Comparative Example 2 as measured after 6 hours

(40) B: allergen protein amount (ng/ml) on the processed sheet using the light-curable coating material of Comparative Example 3 as measured after 6 hours.

(41) <Evaluation of Heat Resistance (Resistance to Discoloration Under Heat)>

(42) Each processed sheet was maintained at 80° C. for 96 hours. After the testing, the sheet was measured for color difference ΔE with a color-difference meter. Evaluations were made according to the following criteria.

(43) ΔE≦1: Excellent

(44) 1<ΔE<2: Good

(45) ΔE≧2: Poor

(46) <Evaluation of Lightfastness (Resistance to Discoloration Under Light)>

(47) Each processed sheet was irradiated in a fade test (Xe lamp) for 48 hours. After the testing, the sheet was measured for color difference ΔE with a color-difference meter. Evaluations were made according to the following criteria.

(48) ΔE≦0.5: Excellent

(49) 0.5<ΔE<1: Good

(50) ΔE≧1: Poor

(51) <Evaluation of Chemical Resistance>

(52) An alkali detergent (product name: Domestos; Unilever) was dropped onto each processed sheet, and the presence or absence of any abnormality in appearance was checked after retention for 24 hours.

(53) TABLE-US-00002 TABLE 2 Hue Percentage Chemical (Coloring allergen Heat resistance property) reduction resistance Lightfastness (Resistance to (ΔE) (%) (ΔE) (ΔE) alkali detergent) Ex. 6 Good 93.5 Excellent Good No abnormality Ex. 7 Good 85.6 Excellent Good No abnormality Ex. 8 Excellent 91.2 Excellent Excellent No abnormality Com. Ex. 2 Poor 83.4 Poor Poor No abnormality Com. Ex. 3 Good Reference Good Excellent No abnormality (Terpene phenol resin was not mixed)

(54) It was confirmed from the results present in Table 2 that the processed sheets obtained by applying the light-curable coating materials of Examples 6 to 8 had less coloring and superior heat resistance and lightfastness compared to the processed sheet obtained by applying the light-curable coating material of Comparative Example 2 containing a conventional allergen reducing agent. It was also confirmed that the allergen reducing performance and chemical resistance were excellent.

Example 9

(55) A beech lumber single board having a thickness of 0.2 mm was bonded to an 11.8 mm-thick lauan plywood, and a V groove was formed to produce a floor wood base. Then, an aqueous coloring agent was applied to the wood base. After drying the wood base at 80° C. for 1 min, a UV curable urethane acrylate primer coating material was applied to the wood base with a sponge roller. The coating material was scraped off with a metal reverse rotating roller to make the total coating amount 2 g/shaku.sup.2. After further applying the coating in 1 g/shaku.sup.2 with a rubber roller, the coating was cured by UV irradiation at a cumulative illuminance of 100 mJ/cm.sup.2. Thereafter, a UV curable urethane acrylate middle coating material mixed with 30 parts of antifriction white alumina was applied twice with a rubber roller in a total of 2 g/shaku.sup.2 to form a first middle coating, and the coating was cured by UV irradiation at a cumulative illuminance of 200 mJ/cm.sup.2. This was followed by polishing with a #320 sandpaper. Thereafter, a UV curable urethane acrylate middle coating material was applied with a sponge roller and a rubber roller in a total of 2 g/shaku.sup.2, and then with a flow coater in 7 g/shaku.sup.2 to form a second middle coating. The coating was then cured by UV irradiation at a cumulative illuminance of 100 mJ/cm.sup.2.

(56) Further, the light-curable coating material obtained in Example 6 was applied with a rubber roller in 1 g/shaku.sup.2, and cured by UV irradiation at a cumulative illuminance of 350 mJ/cm.sup.2 to produce a wood floor material.

Example 10

(57) A wood floor material was produced in the same manner as in Example 9, except that the light-curable coating material obtained in Example 7 was used instead of the light-curable coating material obtained in Example 6 which was used in Example 9.

Example 11

(58) A wood floor material was produced in the same manner as in Example 9, except that the light-curable coating material obtained in Example 8 was used instead of the light-curable coating material obtained in Example 6 which was used in Example 9.

Example 12

(59) A pictorial pattern layer (2 μm) was formed on 0.06 mm-thick colored polypropylene (base sheet) by printing. Then, a 0.08 mm-thick transparent polypropylene resin film was bonded onto the pictorial pattern layer with a urethane-based dry laminate adhesive to form a transparent resin layer. Thereafter, the light-curable coating material obtained in Example 6 was applied onto the transparent resin layer with a rubber roller in 1 g/shaku.sup.2. The coating was then irradiated with UV rays at a cumulative illuminance of 350 mJ/cm.sup.2 to produce a decorative sheet.

(60) Then, a urethane-based adhesive was applied to the back surface of the decorative sheet, and a PP resin backer layer was attached. A wood base composed of plyboard wood base was then bonded to the back side of the backer layer using a urethane-modified ethylene-vinyl acetate emulsion adhesive to produce a wood floor material.

Example 13

(61) <Allergen Reducing Agent-Containing Coating Material>

(62) An allergen reducing agent-containing coating material was obtained by adding and stirring the allergen reducing agent, specifically the terpene phenolic resin YS Polyster T130 (Yasuhara Chemical; 10 weight parts), urethane acrylate (product name: Shikou 7550B; Nippon Synthetic Chemical Industry Co., Ltd.; 30 weight parts), trimethylolpropane triacrylate (EO addition; product name: M310; Toagosei Co., Ltd.; 20 weight parts), 1,9-nonanediol diacrylate (product name: L-9CA; Dai-Ichi Kogyo Seiyaku Co., Ltd.; 50 weight parts), hydrophobic silica (product name: Sylophobic 702; Fuji Silysia Chemical Ltd.; 5 weight parts), and acrylic beads (product name: GM0401S; Ganz Chemical Co., Ltd.; 5 weight pans).

(63) <Wood Floor Material with Allergen Reducing Agent-Containing Coating Material Applied Thereon>

(64) A pictorial pattern layer (2 μm) was formed on a 0.06 mm-thick colored polypropylene sheet (base sheet) by printing. Then, a 0.08 mm-thick transparent polypropylene resin film was bonded onto the pictorial pattern layer using a urethane-based dry laminate adhesive. Thereafter, the allergen reducing agent-containing coating material was applied onto the transparent resin layer with a rubber roller in 1 g/shaku.sup.2. The coating was then cured by irradiation of 30 kGy electron rays at an acceleration voltage of 125 eV to produce a decorative sheet.

(65) Then, a urethane-based adhesive was applied to the back surface of the decorative sheet, and a PP resin backer layer was attached. A wood base composed of plyboard wood base was then bonded to the back side of the backer layer using a urethane-modified ethylene-vinyl acetate emulsion adhesive to produce a wood floor material.

Comparative Example 4

(66) A wood floor material was produced in the same manner as in Example 9, except that the light-curable coating material obtained in Comparative Example 2 was used instead of the light-curable coating material obtained in Example 6 which was used in Example 9.

Comparative Example 5

(67) An allergen reducing agent-containing coating material was produced in the same manner as in Example 13, and a wood floor material was also produced in the same manner as in Example 13, except that the polyvinylphenolic resin Maruka Lyncur M was used instead of the terpene phenolic resin YS Polyster T130 used in Example 13.

Comparative Example 6

(68) A wood floor material was produced in the same manner as in Example 9, except that the light-curable coating material obtained in Comparative Example 3 was used instead of the light-curable coating material obtained in Example 6 which was used in Example 9.

Comparative Example 7

(69) An allergen reducing agent-containing coating material was produced in the same manner as in Example 13, and a wood floor material was also produced in the same manner as in Example 13, except that the terpene phenolic resin YS Polyster T130 used in Example 13 was not mixed.

(70) The wood floor materials obtained in Examples 9 to 13 and Comparative Examples 4 to 7 were measured for hue (coloring property), allergen reducing performance, heat resistance (resistance to discoloration under heat), lightfastness (resistance to discoloration under light), and chemical resistance. The results are presented in Table 3.

(71) The hue (coloring property), heat resistance (resistance to discoloration under heat), and lightfastness (resistance to discoloration under light) were measured and evaluated by using the same methods and according to the same criteria used for the processed sheets, and explanations thereof are omitted.

(72) <Measurement of Allergen Reducing Performance>

(73) 1) Preparation of Allergen Solution

(74) An allergen solution was produced by dissolving an allergen freeze dried powder (purified mite antigen; Der2; Asahi Breweries Ltd.) in a phosphate buffer (pH7.6) so as to provide an allergen protein amount of 20 ng/ml.

(75) 2) Reaction

(76) The allergen solution prepared in procedure 1) was dropped onto the wood floor materials prepared in Examples 9 to 13 and Comparative Examples 4 to 7 in 400 μl portions, and the allergen protein amount was measured with an ELISA kit (Indoor) after 6 hours of reaction. The percentage allergen reduction was calculated as follows.
Percentage allergen reduction (%)=100×(1−A/B)

(77) A: allergen protein amount (ng/ml) on the wood floor materials of Examples 9 to 13 and Comparative Examples 4 and 5 as measured after 6 hours

(78) B: allergen protein amount (ng/ml) on the wood floor material of Comparative Examples 6 and 7 as measured after 6 hours.

(79) <Evaluation of Chemical Resistance>

(80) An alkali detergent (product name: Domestos; Unilever) was dropped onto each wood floor material obtained in Examples 9 to 13 and Comparative Examples 4 to 7, and the presence or absence of any abnormality in appearance was checked after retention for 24 hours. Evaluations were made according to the following criteria.

(81) No abnormality in appearance: Good

(82) Abnormality in appearance (yellowing): Poor

(83) TABLE-US-00003 TABLE 3 Hue Percentage Chemical Coloring allergen Heat resistance property) reduction resistance Lightfastness (Resistance to (ΔE) (%) (ΔE) (ΔE) alkali detergent) Ex. 9 Good 93.5 Excellent Good Good Ex. 10 Good 85.6 Excellent Good Good Ex. 11 Excellent 91.2 Excellent Excellent Good Ex. 12 Good 92.1 Excellent Good Good Ex. 13 Good 89.5 Excellent Excellent Good Com. Ex. 4 Poor 83.4 Poor Poor Good Com. Ex. 5 Poor 25.3 Poor Excellent Poor (Turned yellow) Com. Ex. 6 Excellent Reference Good Excellent Good (Terpene phenol resin was not mixed) Com. Ex. 7 Excellent Reference Good Excellent Good (Terpene phenol resin was not mixed)

(84) It was confirmed from the results presented in Table 3 that the wood floor materials of Examples 9 to 13 had excellent allergen reducing performance, less coloring, and excellent heat resistance (resistance to discoloration under heat), lightfastness, and chemical resistance.