Polyurethane foam, process for producing the same, and foam forming composition

A polyurethane foam which is obtained by reacting an addition-polymerizable polymerizable active hydrogen component (A) comprising a compound (A1) with or without not more than 80 mass % of a compound (A0) based on a total mass of the compounds (A1) and (A0), or comprising a compound (A1) and a compound (A2) with or without not more than 80 mass % of a compound (A0) based on the total mass of the compounds (A1) and (A0), with

• an organic polyisocyanate (B) in the presence or absence of at least one auxiliary (C) selected from the group consisting of blowing agents (C1) and additives (C2) to polymerize the addition-polymerizable which addition polymerization functional group and simultaneously form a polyurethane under a condition in which addition polymerization chains and polyurethane chains are crosslinked;
• the compound (A1) having at least one group containing active hydrogen (w) and at least one addition-polymerizable functional group (x) represented by a general formula (1);
• the compound (A2) having at least 2.5 groups (w) and not having the group (x);
• the compound (A0) containing an addition-polymerizable functional group and not having an active hydrogen-containing group;
• wherein in the case of using a combination of the compounds (A1) and (A2) in the component (A) it is selected from 1to 3, wherein
• {circle around (1)} is a compound (A11) having one group (w) as the compound (A1), and a compound with a value of active hydrogen-containing group of at least 40as the compound (A2);
• {circle around (2)} is a compound (A12) having at least two groups (w) as the compound (A1), and the compound (A2);
• {circle around (3)} is a compound (A11), the compound (A12), and the compound (A2);
• wherein an amount of (A12) being at least 5 mass % based on a total mass of the compounds (A11) and (A12);
• wherein (1)is
• wherein R denotes hydrogen, an alkyl group having 1to 15carbon atoms, or an aryl group having 6 to 21 carbon atoms;
• wherein (A1) is a compound selected from compounds (A1/1) to (A1/4), wherein
• (A1/1) are partial esters of an unsaturated carboxylic acid with a polyol selected from polyols (i) to (vi), wherein
• (i) are dihydric alcohols;
• (ii) are alcohols with a value of 3 to 8 selected from glycerol, trimathylolpropane, pentaerythritol, diglycerol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, and sucrose;
• (iii) are polyhydric phenols;
• (iv) are polyether polyols derived from alkylene oxiders with a polyhydric alcohol or a polyhydric phenol;
• (v) are polyether polyols derived from alkylene oxiders with an amine;
• (vi) are polyester polyols derived from a polyhydric alcohol and a polycarboxylic acid,
• (A1/2) are partially amidated compounds derived from an unsaturated acid and a polyamine, or alkanolamides derived from an unsaturated carboxylic acid and an alkanolamine;
• (A1/3) are partial thioesters of an unsaturated carboxylic acid with a polythiol;
• (A1/4) are vinyl monomers having a hydroxyl group selected from p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl alcohol, and alkylene oxide adducts of these compounds.

A polyurethane foam comprising an elastic polyurethane foam obtained by reacting an addition-polymerizable active hydrogen componenet (A') with an organic polyisocyanate (B) in the presence or absence of at least one auxiliary (C) selected from the group consisting of blowing agents (C1) and additives (C2) to polymerize the addition-polymerizable functional group and simultaneously form a polyurethane under condition in which addition polymerization chains and polyurethane chains are crosslinked.

• addition-polymerizable active hydrogen component (A') is an addition-polymeriazable active hydrogen component which comprises an active hydrogen-containing group (w) and an addition-polymerizable functional group (x) and which is selected from (A31), (A32), and (A33);
• wherein a reaction rate constant K1 between the active hydrogen-containing group (w) and an isocyanate group (z) at 120 ° C. is not more than 1 (liter/mol/sec);
• a polymerization reaction rate constant K2 of the addition-polymerizable functional group (x) is not less than 10 (liter/mol/sec);
• and K2/K1 is not less than 100, wherein
• (A31) is an addition-polymerizable active hydrogen compound which has an active hydrogen-containing group (w) and an addition-polymerizable functional group (x), and which may have a cyclic group (y) reactive with the group (w);
• (A32) is an active hydrogen compound (A321) having at least three groups (w) or having the groups (w) and (y), and an addition-polymerizable compound (A322) having the groups (x) and (y), used in combination;
• (A33) is compound (A31) and the compound (A322), used in combination;
• wherein a compound (A311) having an active hydrogen-containing group (w) and an addition-polymerizable functional group (x) among the compound (A31) has a group (x) represented by a following general formula (1) and is selected from (A1/1) to (A1/4), wherein (1) is
• wherein R denotes hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms;
• wherein (A1) is a compound selected from compounds (A1/1) to (A1/4), wherein
• (A1/1) are partial esters of an unsaturated carboxylic acid with a polyol selected from polyols (i) to (vi), wherein
• (i) are dihydric alcohols;
• (ii) are alcohols with a value of 3 to 8 selected from glycerol, trimethylolpropane, pentaerythrit, diglycerol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, and sucrose;
• (iii) are polyhydric phenols;
• (iv) are polyether polyols derived from alkylene oxiders with a polyhydric alcohol or a polyhydric phenol;
• (v) are polyether polyols derived from alkylene oxiders with an amine;
• (vi) are polyester polyols derived from apolyhydric alcohol and a polycarboxylic acid;
• (A1/2) are partially amidated compounds derived from an unsaturated carboxylic acid and a polyamine, or alkanolamiders derived from an unsaturted carboxylic acid and an alkanolamine;
• (A1/3) are partial thioesters of an unsaturated carboxylic acid with polythiol;
• (A1/4) are vinyl monomers having a hydroxyl group selected from p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl alcohol, and alkylene oxide adducts of these compounds.

A process for producing a polyurethane foam which comprises reacting an addition-polymerizable active hydrogen component (A) comprising a compound (A1) with or without not more than 80 mass % of a compound (A0) based on a total mass of the compounds (A1) and (A0), or comprising a compound (A1) and a compound (A2) with or without not more than 80 mass % of a compound (A0) based on the total mass of the compounds (A1) and (A0), with

• an organic polyisocyanate (B) in the presence or absence of at loeast one auxiliary (C) selected from the group consisting of blowing agents (C1) and additives (C2) to polymerize the addition-polymerizable functional group and simultaneously form a polyurethane under a condition in which addition polymerization chains and polyurethane chains are crosslinked;
• the compound (A1) having at least one group containing active hydrogen (w) and at least one addition-polymerizable functional group (x) represented by a general formula (1);
• the compound (A2) having at least 2.5 groups (w) and not having the group (x);
• the compound (A0) containing an addition-polymerizable functional group and not having an active hydrogen-containing group;
• wherein in the case of using a combination of the compounds (A1) and (A2) in the component (A) it is selected from 1 to 3, wherein
• {circle around (1)} is a compound (A11) having one group (w) as the compound (A1), and a compound with a value of active hydrogen-containing group of at least 40 as the compound (A2);
• {circle around (2)} is a compound (A12) having at least two groups (w) as the compound (A1), and the compound (A2);
• {circle around (3)} is the compound (A11), the compound (A12), and the compound (A2);
• wherein an amount of (A12) being at leastk 5 mass % based on a total mass of the compounds (A11) and (A12);
• wherein (1) is
• wherein R denotes hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms;
• wherein (A1) is a compound selected from compounds (A1/1) to (A1/4), wherein
• (A1/1) are partial esters of an unsaturated carboxylic acid with a polyol seleded from polyols (i) to (vi), wherein
• (i) are dihydric alcohol;
• (ii) are alcohols with a value of 3 to 8 selected from glycerol, trimethylolpropane, pentaerythritol, diglycerol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, and sucrose;
• (iii) are polyhydric phenols;
• (iv) are polyether polyols derived from alkylene oxides with a polyhydric alcohol or a polyhydric phenol;
• (v) are polyether polyols derived from alkylene oxides with an amine;
• (vi) are polyester polyols derived from a polyhydric alcohol and a polycarboxylic acid;
• (A1/2) are partially amidated compounds derived from an unsaturated carboxylic acid and a polyamine, or alkanolamides derived from an unsaturated carboxylic acid and an alkanolamine;
• (A1/3) are partial thioester of an unsaturated carboxylic acid with a polythiol;
• (A1/4) are vinyl monomers having a hydroxyl group selected from a p-hydroxylstyrene, (meth)ally alcohol, cinnamyl alcohol, crotonyl alcohol, and alkylene oxide adducts of these compounds.

A composition for forming a polyurethane foam which comprises an addition-polymerizable active hydrogen component (A) comprising a compound (A1) with or without not more than 80 mass % of a compound (A0) based on a total mass of the compounds (A1) and (A0), or comprising a compound (A1) and a compound (A2) with or without not more than 80 mass % of a compound (A0) based on the total mass of the compounds (A_b 1) and (A0);

• the compound (A1) having at least one group containing active hydrogen (w) and at least one addition-polymerizable functional group (x) represented by a general formula (1);
• the compound (A2) having at least 2.5 groups (w) and not having the group (x);
• the compound (A0) containing an addition-polymerizable functional group and not having an active hydrogen-containing group, and
• an organic polyisocyanate (B), and which comprises or does not comprise at least one auxiliary (C) selected from the group consisting of blowing agents (C1) and additives (C2), wherein in the case of using a combination of the compounds (A1) and (A2) in the component (A) it is selected from 1 to 3,wherein
• {circle around (1)} is a compound (A11) having one group (w) as the compound (A1), and a compound with a value of active hydrogen-containing group of at least 40 as the compound (A2);
• {circle around (2)} is a compound (A12) having at least two groups (w) as the compound (A1), and the compound (A2);
• {circle around (3)} is the compound (A11), the compound (A12), and the compound (A2);
• wherein an amount of (A12) being at least 5 mass % based on total mass of the compounds (A11) and (A12);
• wherein (1) is
• wherein R denotes hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6to 21 carbon atoms;
• wherein (A1) is a compound selected from compounds (A11) and
• (A1/1) are partial esters of an unsaturated carboxylic acid with a polyol selected from polyols (i) to (vi), wherein
• (i) are dihydric alcohols;
• (ii) are alcohols with a value of 3 to 8 selected from glycerol, trimethylolpropane, pentaerythritol, diglycerol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, and sucrose;
• (iii) are polyhydric phenols;
• (iv) are polyether polyols derived from alkylene oxides with a polyhydric alcohol or a polyhydric phenol;
• (v) are polyether polyols derived from alkylene oxides with an amine;
• (vi) are polyester polyols derived from a polyhydric alcohol and a polycarboxylic acid;
• (A1/2) are partially amidated compounds derived from an unsaturated carboxylic acid and a polyamine, or alkanolamides derived from an unsaturated carboxylic acid and an alkanolamine;
• (A1/3) are partial thioesters of an unsaturated carboxylic acid with a polythiol;
• (A1/4) are vinyl monomers having a hydroxyl group selected from p-hydrocylstyrene, meth)allyl alcohol, cinnamyl alcohol, crotonyl alcohol, and alkylene oxide adducts of these compounds.

An addition-polymerizable active hydrogen component for forming a polyurethane foam which comprises a compound (A1) with or without not more than 80 mass % of a compound (A0) based on a total mass of the compounds (A1) and (A0), or comprises a compound (A1) and a compound (A2) with or without not more than 80 mass % of a compound (A0) based on the total mass of the compounds (A10 and (A0);

• the compound (A1) having at least one group (x) repreesented by a general formula (1);
• the compound (A2) having at least 2.5 groups (w) and not having the group (x);
• the compound (A0) containing an addition-polymerizable functional group and not having an active hydrogen-containing group, and wherein in the case of using a combination of the compounds (A1) and (A2) it is selected from 1 to 3,wherein
• {circle around (1)} is a compound (A11) having one group (w) as the compound (A1), and a compound with a value of active hydrogen-containing group of at least 40 as the compound (A2);
• {circle around (2)} is a compound (A12) having at least two groups (w) as the compound (A10, and the compound (A2);
• {circle around (3)} is the compound (A11), the compound (A12), and the compound (A2);
• wherein an amount of (A12) being at least 5mass % based on a total mass of the compounds (A11) and (A12);
• wherein R denotes hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms;
• wherein (A1) is a compound selected from compounds (A1/1) to (A1/4), wherein (A1/1) are partial esters of an unsaturated carboxylic acid with a polyol selected from polyols (i) to (vi), wherein
• (i) are dihydric alcohols;
• (ii) are alcohols with a value of 3 to 8 selected from glycerol, trimethylolpropane, pentaerythritol, diglycerol, α-methylglucoside, sorbitol, xylitol, mannitol, glucose, fructose, and sucrose;
• (iii) are polyhydric phenols;
• (iv) are polyether polyols derived from alkylene oxides with a polyhydric alcohol or a polyhydric phenol;
• (v) are polyether polyols derived from alkylene oxides with an amine;
• (vi) are polyester polyols derived from polyhydric alcohol and a polycarboxylic acid;
• (A1/2) are partial thioesters of an unsaturated carboxylic acid and a
• polyamine, or alkanolamides derived from an unsaturated carboxylic acid and an alkanolamine;
• (A1/3) are partial thioesters of an unsaturated carboxylic acid with a polythiol;
• (A1/4) are vinyl monomers having a hydroxyl group selected from p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl alcohol, and alkylene oxide adducts of these compounds.