Disclosed is a support material for a fused deposition modeling. The support material has excellent adhesion to a variety of model materials and is easily dissolved and removed by washing with water. Also, the waste liquid (PVA-based aqueous solution) generated after the washing operation may be allowed to be drained as it is, in compliance with environmental regulations. The support material comprises (A) PVA-based resin having a group containing sulfonic acid or a salt thereof and (B) biodegradable polyester. The (A) PVA-based resin having a group containing sulfonic acid or a salt thereof and (B) biodegradable polyester have a sea-island structure in which one is dispersed in the other as a matrix.

Regarding the oxyalkylene group-containing PVA-based resin, a package which is almost free from a problem associated with viscosity increase during melt-kneading even if the package is stored for a long time period, and a method for manufacturing the package are disclosed. The package comprises a bag having an oxygen permeability of 1000 cc/m.sup.2.Math.day.Math.atm or less as an amount of oxygen permeated in 24 hours per 1 m.sup.2 of its constituent film under an condition of 25° C. and 65% RH, and an oxyalkylene group-containing PVA-based resin in the bag. The package can suppress the oxidation of the oxyalkylene group-containing PVA and the generation of the carboxyl group-containing compound which may cause to increase viscosity during melt kneading.

Regarding the oxyalkylene group-containing PVA-based resin, a package which is almost free from a problem associated with viscosity increase during melt-kneading even if the package is stored for a long time period, and a method for manufacturing the package are disclosed. The package comprises a bag having an oxygen permeability of 1000 cc/m.sup.2.Math.day.Math.atm or less as an amount of oxygen permeated in 24 hours per 1 m.sup.2 of its constituent film under an condition of 25° C. and 65% RH, and an oxyalkylene group-containing PVA-based resin in the bag. The package can suppress the oxidation of the oxyalkylene group-containing PVA and the generation of the carboxyl group-containing compound which may cause to increase viscosity during melt kneading.

Regarding the oxyalkylene group-containing PVA-based resin, a package which is almost free from a problem associated with viscosity increase during melt-kneading even if the package is stored for a long time period, and a method for manufacturing the package are disclosed. The package comprises a bag having an oxygen permeability of 1000 cc/m.sup.2.Math.day.Math.atm or less as an amount of oxygen permeated in 24 hours per 1 m.sup.2 of its constituent film under an condition of 25° C. and 65% RH, and an oxyalkylene group-containing PVA-based resin in the bag. The package can suppress the oxidation of the oxyalkylene group-containing PVA and the generation of the carboxyl group-containing compound which may cause to increase viscosity during melt kneading.

A sulfonic acid modified polyvinyl alcohol resin comprising up to 15 mol % of a first comonomer comprising sulfonic acid groups. The modified polyvinyl alcohol resin has a hydroxyl unit content of at least 65 mol % and a gel fraction of 3.2 or less. Further, the modified polyvinyl alcohol resin has a disintegration time of 85 seconds or less, as measured in a mixture of 50 vol % water and 50 vol % isopropyl alcohol at 23° C. Additionally, the modified polyvinyl alcohol resin has a hard component present in a component ratio of 10% or greater and 55% or less and having a relaxation time of 0.0091 milliseconds or greater and 0.0104 milliseconds or less, as measured by the pulsed NMR Solid Echo method at 80° C. Also disclosed are methods for producing the sulfonic acid modified polyvinyl alcohol resins, which may advantageously be used in inks, paints, paper coatings, emulsions, or films.

A sulfonic acid modified polyvinyl alcohol resin comprising up to 15 mol % of a first comonomer comprising sulfonic acid groups. The modified polyvinyl alcohol resin has a hydroxyl unit content of at least 65 mol % and a gel fraction of 3.2 or less. Further, the modified polyvinyl alcohol resin has a disintegration time of 85 seconds or less, as measured in a mixture of 50 vol % water and 50 vol % isopropyl alcohol at 23° C. Additionally, the modified polyvinyl alcohol resin has a hard component present in a component ratio of 10% or greater and 55% or less and having a relaxation time of 0.0091 milliseconds or greater and 0.0104 milliseconds or less, as measured by the pulsed NMR Solid Echo method at 80° C. Also disclosed are methods for producing the sulfonic acid modified polyvinyl alcohol resins, which may advantageously be used in inks, paints, paper coatings, emulsions, or films.

A sulfonic acid modified polyvinyl alcohol resin comprising up to 15 mol % of a first comonomer comprising sulfonic acid groups. The modified polyvinyl alcohol resin has a hydroxyl unit content of at least 65 mol % and a gel fraction of 3.2 or less. Further, the modified polyvinyl alcohol resin has a disintegration time of 85 seconds or less, as measured in a mixture of 50 vol % water and 50 vol % isopropyl alcohol at 23° C. Additionally, the modified polyvinyl alcohol resin has a hard component present in a component ratio of 10% or greater and 55% or less and having a relaxation time of 0.0091 milliseconds or greater and 0.0104 milliseconds or less, as measured by the pulsed NMR Solid Echo method at 80° C. Also disclosed are methods for producing the sulfonic acid modified polyvinyl alcohol resins, which may advantageously be used in inks, paints, paper coatings, emulsions, or films.

A hydrophilic polymer comprising pendent groups of the formula I: Wherein: W is independently selected from —OH, —COOH, —SO.sub.3H, —OPO.sub.3H, —O—(C.sub.1-4alkyl), —O—(C.sub.1-4alkyl)OH, —O—(C.sub.1-4alkyl)R.sup.2, —O—(C.sub.2H.sub.5O).sub.qR.sup.1—(C═O)—O—C.sub.1-4alkyl and —O—(C═O)C.sub.1-4alkyl; or a group —BZ; wherein —OH, COOH, O—PO.sub.3H and SO.sub.3H maybe in the form of a pharmaceutically acceptable salt; wherein: B is a bond, or a straight branched alkanediyl, oxyalkylene, alkylene oxaalkylene, or alkylene (oligooxalkylene) group, optionally containing one or more fluorine substituents; and Z is an ammonium, phosphonium, or sulphonium phosphate or phosphonate ester zwitterionic group; X is either a bond or a linking group having 1 to 8 carbons and optionally 1 to 4 heteroatoms selected from O, N and S; G is a coupling group through which the group of the formula I is coupled to the polymer and is selected from ether, ester, amide, carbonate, carbamate, 1,3 dioxolone, and 1,3 dioxane; R.sup.1 is H or C.sub.1-4 alkyl; R.sup.2 is —COOH, —SO.sub.3H, or —OPO.sub.3H.sub.2 q is an integer from 1 to 4; n is an integer from 1 to 4; p is an integer from 1 to 3; and n+p is from 2 to 5; and wherein —COOH, —OPO.sub.3H.sub.2 and —SO.sub.3H as well as phenolic —OH maybe in the form of a pharmaceutically acceptable salt.

A hydrophilic polymer comprising pendent groups of the formula I: Wherein: W is independently selected from —OH, —COOH, —SO.sub.3H, —OPO.sub.3H, —O—(C.sub.1-4alkyl), —O—(C.sub.1-4alkyl)OH, —O—(C.sub.1-4alkyl)R.sup.2, —O—(C.sub.2H.sub.5O).sub.qR.sup.1—(C═O)—O—C.sub.1-4alkyl and —O—(C═O)C.sub.1-4alkyl; or a group —BZ; wherein —OH, COOH, O—PO.sub.3H and SO.sub.3H maybe in the form of a pharmaceutically acceptable salt; wherein: B is a bond, or a straight branched alkanediyl, oxyalkylene, alkylene oxaalkylene, or alkylene (oligooxalkylene) group, optionally containing one or more fluorine substituents; and Z is an ammonium, phosphonium, or sulphonium phosphate or phosphonate ester zwitterionic group; X is either a bond or a linking group having 1 to 8 carbons and optionally 1 to 4 heteroatoms selected from O, N and S; G is a coupling group through which the group of the formula I is coupled to the polymer and is selected from ether, ester, amide, carbonate, carbamate, 1,3 dioxolone, and 1,3 dioxane; R.sup.1 is H or C.sub.1-4 alkyl; R.sup.2 is —COOH, —SO.sub.3H, or —OPO.sub.3H.sub.2 q is an integer from 1 to 4; n is an integer from 1 to 4; p is an integer from 1 to 3; and n+p is from 2 to 5; and wherein —COOH, —OPO.sub.3H.sub.2 and —SO.sub.3H as well as phenolic —OH maybe in the form of a pharmaceutically acceptable salt.

A preparation method of a hydrogel of a mercapto-modified macromolecular compound includes the steps of combining the mercapto-modified macromolecular compound with an acrylated macromolecular compound and/or an acrylated micromolecular crosslinker. The mercapto-modified macromolecular compound can be crosslinked with the acrylated macromolecular compound and/or the acrylated micromolecular crosslinker under physiological conditions to form the hydrogel. Due to the rapid mercapto-vinyl crosslinking reaction, the formed hydrogel system can be quickly gelled in situ after being injected into the body. The hydrogel is thus suitable for use in the fields of biomedicine, medical cosmetic plastic surgery and cosmetics.