WO2023042923A1

WO2023042923A1 - Foam stabilizer for polyurethane foam, polyurethane foam, and polyurethane foam laminate, and methods for producing same

Info

Publication number: WO2023042923A1
Application number: PCT/JP2022/034979
Authority: WO
Inventors: 康弘大岩; 卓暉鬼澤
Original assignee: 楠本化成株式会社
Priority date: 2021-09-17
Filing date: 2022-09-20
Publication date: 2023-03-23

Abstract

[Problem] To provide: a foam stabilizer that is for polyurethane foam, and that has, without using a silicone-based foam stabilizer, a foam stabilizing ability comparable to or better than that of a silicone-based foam stabilizer, and can provide, to a polyurethane foam, a sufficient adhesive strength with respect to even a hardly-adhesive base material such as polypropylene resins; a polyurethane foam obtained by using said foam stabilizer; a polyurethane foam laminate obtained by laminating said polyurethane foam on the surface of a base material; and methods for producing same. [Solution] This foam stabilizer is for a polyurethane foam and is to be mixed with a polyisocyanate and a polyol for use in production of a polyurethane foam. The foam stabilizer contains a copolymer including 5-95 mass% of a structural unit derived from a polymerizable unsaturated monomer (A) that includes an ether group and 5-95 mass% of a structural unit derived from a polymerizable unsaturated monomer (B) that includes a hydrophobic group.

Description

Foam stabilizer for polyurethane foam, polyurethane foam and polyurethane foam laminate, and method for producing the same

The present invention relates to a foam stabilizer for polyurethane foams, polyurethane foams, polyurethane foam laminates, and methods for producing these.

Polyurethane foam is made by mixing polyisocyanate with NCO (isocyanate) groups and polyol with OH (hydroxyl) groups together with catalysts, foaming agents, foam stabilizers, etc., and performing foaming reaction and resinification reaction at the same time. It is a homogeneous plastic foam obtained by applying Polyurethane foams are broadly classified into flexible polyurethane foams (hereinafter referred to as "soft urethane foams") and rigid polyurethane foams (hereinafter referred to as "rigid urethane foams").

A silicone-based foam stabilizer such as silicone oil is generally used as a foam stabilizer used in the production of polyurethane foam (see, for example, Patent Document 1). Patent Document 1 discloses a polyurethane foam foam stabilizer containing at least a polyether-modified silicone compound synthesized by a hydrosilylation reaction between an organohydrogenpolysiloxane and an allyl group-containing polyoxyalkylene compound. .

In addition, rigid urethane foam has an excellent feature of self-adhesion. Due to this self-adhesiveness, a mixture of polyisocyanate, polyol, catalyst, foaming agent, foam stabilizer, etc. is directly foamed on the surface of the object (base material) such as metal, plywood, concrete, etc. to generate rigid urethane foam. As a result, a heat insulating layer strongly adhered to the object can be formed without using an adhesive.

JP 2007-186557 A

However, attempts have been made to self-adhesively bond rigid urethane foam to the surface of difficult-to-adhere base materials such as base materials such as polypropylene resin, polyethylene resin, fluororesin, and silicone resin, and base materials coated with wax. However, sufficient adhesive strength cannot be obtained. As for the cause, according to the studies by the present inventors, it was found that one of the factors is the silicone-based foam stabilizer used in most polyurethane foams.

In addition, there are concerns that the cyclic siloxane contained in the silicone-based foam stabilizer diffuses into the air, causing damage to electrical and electronic circuits and affecting semiconductor production lines. Furthermore, in Europe and the United States, cyclic siloxanes are considered to be environmental pollutants, and the reduction of emissions and restrictions on their use are being considered.

Therefore, the present invention has been made in view of the above circumstances, and has a foam stabilizing ability equal to or higher than that of a silicone foam stabilizer without using a silicone foam stabilizer, and a polypropylene resin or the like. A foam stabilizer for polyurethane foam capable of imparting sufficient adhesive strength to a polyurethane foam even to a difficult-to-adhere substrate, a polyurethane foam obtained using this foam stabilizer, and a laminate of this polyurethane foam on the surface of a substrate An object of the present invention is to provide polyurethane foam laminates and methods for producing them.

The present inventors have made intensive studies to solve the above problems, and found that a copolymer of a specific polymerizable unsaturated monomer having an ether group and a specific polymerizable unsaturated monomer having a hydrophobic group. A polyurethane foam that, when used as a foam stabilizer, has a foam-stabilizing ability equal to or greater than that of a silicone-based foam stabilizer, and that can impart sufficient adhesive strength to polyurethane foam even to difficult-to-adhere substrates such as polypropylene resin. The present inventors have found that a foam stabilizer can be obtained, and have completed the present invention based on this finding.

That is, the present invention provides a foam stabilizer for polyurethane foam which is mixed with a polyisocyanate and a polyol and used for the production of polyurethane foam, wherein the structural unit derived from the polymerizable unsaturated monomer (A) is % by mass, and a copolymer containing 5 to 95% by mass of structural units derived from the polymerizable unsaturated monomer (B), and the polymerizable unsaturated monomer (A) is represented by the following general formula (1 ), and the polymerizable unsaturated monomer (B) is a polymerizable unsaturated monomer group that does not satisfy the general formula (1) and has a hydrophobic group A foam stabilizer for polyurethane foam, which is at least one monomer selected from the above.
R1-( _CmH2mO ) _n -R2 ₍ 1)
(In the general formula (1), R1 is a (meth)acrylic group, R2 is a hydrogen atom, a (meth)acrylic group, or an alkyl or aryl group having 1 to 22 carbon atoms, and m is A natural number of 2 to 4, and n is a natural number of 1 to 100.)

In another aspect of the present invention, the SP value of the foam stabilizer for polyurethane foam is preferably 1.0 to 3.1 lower than the SP value of the polyol.

In one aspect of the present invention, the copolymer may have a weight average molecular weight of 1,000 to 500,000.

In another aspect of the present invention, the copolymer contains, as the polymerizable unsaturated monomer (A), only polymerizable unsaturated monomers in which R1 in the general formula (1) is a (meth)acrylic group. is preferred.

In another aspect of the present invention, the hydrophobic group of the polymerizable unsaturated monomer (B) may be a linear, branched or cyclic hydrocarbon group.

In another aspect of the present invention, the hydrophobic group of the polymerizable unsaturated monomer (B) may be free of oxygen atoms, nitrogen atoms, fluorine atoms and silicon atoms.

Further, the present invention is obtained by foaming and curing a urethane raw material mixture Mu containing at least a polyisocyanate, a polyol, and the foam stabilizer for polyurethane foam described above, and the urethane raw material mixture Mu is obtained by foaming and curing the foam stabilizer Mu. A polyurethane foam containing 0.1% by mass to 5.0% by mass.

In one aspect of the present invention, the SP value of the foam stabilizer is preferably 1.0 to 3.1 lower than the SP value of the polyol.

Further, the present invention provides a polyurethane foam lamination in which a substrate selected from the group consisting of polypropylene resin, polyethylene resin, fluororesin and silicone resin, or a substrate coated with wax, and the polyurethane foam described above are laminated. is the body.

The present invention also provides a method for producing a polyurethane foam foam stabilizer mixed with a polyisocyanate and a polyol and used for producing a polyurethane foam, wherein the polymerizable unsaturated monomer (A) is added in an amount of 5 to 95% by mass. , a polymerization step of obtaining a copolymer by copolymerizing a monomer mixture Mm containing 5 to 95% by mass of a polymerizable unsaturated monomer (B), wherein the polymerizable unsaturated monomer (A) is the following general It is at least one ether group-containing monomer represented by formula (1), and the polymerizable unsaturated monomer (B) is a polymerizable unsaturated monomer that does not satisfy general formula (1) and has a hydrophobic group. A method for producing a polyurethane foam foam stabilizer comprising at least one monomer selected from a group of saturated monomers.
R1-( _CmH2mO ) _n -R2 ₍ 1)
(In the general formula (1), R1 is a (meth)acryl group, R2 is a hydrogen atom, (meth)acryl group, an alkyl group having 1 to 22 carbon atoms or an aryl group, and m is 2 is a natural number from ~4, and n is a natural number from 1 to 100.)

In another aspect of the present invention, the SP value of the foam stabilizer is preferably 1.0 to 3.1 lower than the SP value of the polyol.

Further, the present invention includes a foam stabilizer mixing step of mixing a polyol and the foam stabilizer for polyurethane foam described above to obtain a polyol mixture Mo, and foaming and curing while mixing the polyol mixture Mo and a polyisocyanate. and a foam production step of obtaining a polyurethane foam.

Further, the present invention includes a lamination step of laminating a substrate selected from the group consisting of polypropylene resin, polyethylene resin, fluororesin and silicone resin, or a substrate coated with wax, and polyurethane foam, wherein The process WHEREIN: The said polyurethane foam is a manufacturing method of the polyurethane-foam laminated body which is the foam obtained by the manufacturing method of the polyurethane foam mentioned above.

According to the present invention, a copolymer of a specific polymerizable unsaturated monomer having an ether group and a specific polymerizable unsaturated monomer having a hydrophobic group is used as a foam stabilizer in producing a polyurethane foam. To obtain a foam stabilizer for polyurethane foam having a foam stabilizer equal to or higher than that of a silicone-based foam stabilizer, and to impart sufficient adhesion to a difficult-to-adhere base material such as a polypropylene resin to a polyurethane foam. becomes possible.

It is a schematic diagram which shows the shape of the tensile-shear test piece in an Example.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the present invention, "(meth)acrylic group" refers to at least one selected from "acrylic group" and "methacrylic group", and "(meth)acrylate" refers to at least one selected from "acrylate" and "methacrylate". 1 species.

[Foam stabilizer for polyurethane foam]
A foam stabilizer for polyurethane foam according to a preferred embodiment of the present invention is mixed with polyisocyanate, polyol and other components (catalyst, blowing agent, etc.) and used to produce polyurethane foam. The foam stabilizer according to the present invention comprises, as essential components, a copolymer X containing a structural unit A derived from a polymerizable unsaturated monomer (A) and a structural unit B derived from a polymerizable unsaturated monomer (B). contains as More specifically, this copolymer X is composed of a hydrophobic trunk polymer derived from the polymerizable unsaturated monomer (B) and a hydrophilic branch polymer having an ether group derived from the polymerizable unsaturated monomer (A). is a graft copolymer having a molecular skeleton of Thus, by including the copolymer X in the foam stabilizer according to the present invention, it is possible to obtain a foam stabilizer for polyurethane foam having a foam stabilizing ability equal to or greater than that of a silicone-based foam stabilizer. It is possible to impart sufficient adhesive strength to the polyurethane foam even to difficult-to-adhere substrates such as resins and polyethylene resins.

Here, the "foam stabilizing ability" in the present specification means the ability to sufficiently exert the role of the foam stabilizing agent described below, specifically, the foam volume of the polyurethane foam is large and the cell diameter of the polyurethane foam is It means the performance that can reduce The role of the foam stabilizer in the production of polyurethane foam is to improve the compatibility of each component (polyisocyanate, polyol, etc.) of the polyurethane raw material and to lower the surface tension of the mixed solution of the polyurethane raw material. As a result, the gas involved in the mixed solution can be easily dispersed, so that the cells in the foam can be made uniform and stabilized, and coarsening and non-uniformity of the cells can be suppressed. As a result, it is possible to control the foam volume (volume of foam containing cells) and cell diameter of the produced polyurethane foam. The foam volume and cell diameter of these polyurethane foams also greatly affect the physical properties of the polyurethane foam (eg, heat insulation, water resistance, heat resistance, cushioning properties, shock absorption, sound absorption, weight, etc.).

In this specification, the term "difficult-to-adhere base material" refers to a base material that is difficult to bond with a polyurethane foam using a self-adhesive property of a rigid polyurethane foam or a general adhesive. say. Examples of difficult-to-adhere substrates include substrates such as polypropylene resin, polyethylene resin, fluororesin, and silicone resin, and substrates coated with wax. Furthermore, the "adhesive strength" in this specification includes both the adhesive strength based on the self-adhesiveness of rigid polyurethane foam and the adhesive strength with polyurethane foam using a general adhesive. The essential components and optional components contained in the foam stabilizer according to the present invention are described in detail below.

(Polymerizable unsaturated monomer (A))
The polymerizable unsaturated monomer (A) is a polymerizable unsaturated monomer having at least one ether group represented by general formula (1) below. In addition, the "polymerizable unsaturated monomer" in the present invention means "a monomer having a polymerizable unsaturated hydrocarbon group (carbon-carbon double bond or triple bond)".
R1-( _CmH2mO ) _n -R2 ₍ 1)

In the above general formula (1), R1 is a (meth)acryl group, R2 is a hydrogen atom, a (meth)acryl group, an alkyl group having 1 to 22 carbon atoms or an aryl group, and m is 2 to 4 is a natural number, and n is a natural number from 1 to 100.

Examples of the polymerizable unsaturated monomer (A) include (meth)acrylates, allyl ethers, vinyl ethers, and the like.

Examples of (meth)acrylates include polyethylene glycol mono(meth)acrylate, poly(ethylene-propylene)glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, methoxy Polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypoly(ethylene-propylene)glycol (meth)acrylate, methoxypoly(ethylene-tetramethyleneglycol (meth)acrylate, butoxypoly(ethylene-propyleneglycol) (meth)acrylate , octoxypolyethylene glycol (meth)acrylate, lauroxypolyethyleneglycol (meth)acrylate, stearoxypolyethyleneglycol (meth)acrylate, behenyloxypolyethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylate polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like.

Examples of allyl ethers include polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, methoxypolyethylene glycol allyl ether, polyethylene glycol polypropylene glycol monoallyl ether, butoxypolyethylene glycol polypropylene glycol monoallyl ether, polyethylene glycol diallyl ether, and polypropylene glycol. Diallyl ether etc. are mentioned.

Examples of vinyl ethers include polyethylene glycol monovinyl ether and polypropylene glycol monovinyl ether.

The above monomers may be used singly or in combination of two or more.

Among these monomers, as the polymerizable unsaturated monomer (A), R2 in the general formula (1) is a (meth)acryl group, an alkyl group having 1 to 22 carbon atoms or an aryl group having 1 to 22 carbon atoms. is preferred, and an alkyl group having 1 to 22 carbon atoms is more preferred. By using such a polymerizable unsaturated monomer (A), it is possible to enhance the effect of imparting sufficient adhesion to a substrate to the polyurethane foam.

As a constituent monomer of the copolymer X according to the present invention, it is essential to use an ether group-containing polymerizable unsaturated monomer (A) in which R1 in general formula (1) is a (meth)acrylic group. However, as the constituent monomers of the copolymer X, an ether group-containing polymerizable unsaturated monomer in which R1 in the general formula (1) is a vinyl ether group or an allyl group, and a polymerizable unsaturated monomer in which R1 is a (meth)acrylic group It may be used in combination with (A). However, as a constituent monomer of the copolymer X, it is preferable to use alone a polymerizable unsaturated monomer (A) in which R1 is a (meth)acrylic group. As a result, the adhesive strength to the difficult-to-adhere substrate can be increased more than when R1 is used in combination with a polymerizable unsaturated monomer (A) other than a (meth)acrylic group (for example, a vinyl ether group, an allyl group, etc.).

Further, as constituent monomers of the copolymer X according to the present invention, R2 in the general formula (1) is a hydrogen atom, a (meth)acryl group, an alkyl group having 1 to 22 carbon atoms, or an aryl group. It is essential to use a polyunsaturated monomer (A). However, as a constituent monomer of the copolymer X, an ether group-containing polymerizable unsaturated monomer in which R2 in the general formula (1) is a vinyl ether group or an allyl group, R2 is a hydrogen atom, a (meth)acrylic group or a carbon number of 1 It may be used in combination with a polymerizable unsaturated monomer (A) which is an alkyl group or aryl group of ∼22.

The alkyl chain length m of the ether chain of the polymerizable unsaturated monomer (A) is a natural number of 2 or more and 4 or less. If m is 5 or more, the effect as a polar group, that is, the effect of imparting hydrophilicity to the copolymer X may not be expected. It is generally difficult to obtain an ether group-containing polymerizable unsaturated monomer satisfying general formula (1) where m is 5 or more.

The ether chain length n of the polymerizable unsaturated monomer (A) is a natural number of 1 or more and 100 or less, preferably 4 or more and 50 or less, more preferably 4 or more and 23 or less. If n exceeds 100, there is a possibility that the effect of imparting sufficient adhesive strength to the substrate to the polyurethane foam cannot be obtained. Incidentally, it is generally difficult to obtain an ether group-containing polymerizable unsaturated monomer satisfying general formula (1) where n exceeds 100.

The content of the structural unit A derived from the polymerizable unsaturated monomer (A) is 5% by mass or more and 95% by mass or less when the total mass of the structural unit A and the structural unit B is 100% by mass. If the content of the structural unit A is less than 5% by mass, the adhesive strength to difficult-to-bond substrates will be insufficient. On the other hand, if the content of the structural unit A exceeds 95% by mass, the foam stabilizing ability of the foam stabilizer deteriorates. In order to increase the adhesive strength to difficult-to-bond substrates, the content of structural unit A is preferably 10% by mass or more. Moreover, in order to improve the foam stabilizing ability, the content of the structural unit A is preferably 90% by mass or less.

(Polymerizable unsaturated monomer (B))
The polymerizable unsaturated monomer (B) is at least one monomer selected from the group of polymerizable unsaturated monomers that do not satisfy general formula (1) above and have a hydrophobic group. That is, the polymerizable unsaturated monomer (B) is a polymerizable unsaturated monomer that is different from the polymerizable unsaturated monomer (A) and has a hydrophobic group.

The hydrophobic group possessed by the polymerizable unsaturated monomer (B) is, for example, a linear, branched or cyclic hydrocarbon group. Also, the hydrophobic group preferably does not contain any of oxygen, nitrogen, fluorine and silicon atoms. When the hydrophobic group of the polymerizable unsaturated monomer (B) is a functional group such as those described above, it is possible to achieve both high levels of foam stabilizing ability and adhesion to hard-to-adhere substrates.

Examples of the polymerizable unsaturated monomer (B) include (meth)acrylates, vinyl ethers, vinyl esters, dialkyl maleates, dialkyl fumarate, dialkyl itaconate, aromatic hydrocarbon-based vinyl compounds, α-olefin compounds, and the like.

Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, normal propyl (meth)acrylate, isopropyl (meth)acrylate, normal butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary Butyl (meth)acrylate, hexyl (meth)acrylate, normal octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, normal decyl (meth)acrylate, isodecyl (meth)acrylate Acrylates, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Isostearyl (meth)acrylate, Oleyl (meth)acrylate, Behenyl (meth)acrylate, Benzyl (meth)acrylate, Cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate etc.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, tertiary butyl vinyl ether, normal octyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, behenyl vinyl ether and the like. Examples of vinyl esters include vinyl acetate, vinyl neononanoate, vinyl 2,2-dimethyloctanoate, and vinyl neoundecanoate.

Examples of dialkyl maleates include dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dilauryl maleate, and distearyl maleate. Examples of dialkyl fumarate include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, di-2-ethylhexyl fumarate, dilauryl fumarate, and distearyl fumarate. Furthermore, examples of the dialkyl itaconate include dimethyl itaconate, dibutyl itaconate, di-2-ethylhexyl itaconate, dilauryl itaconate, and distearyl itaconate.

Examples of aromatic hydrocarbon-based vinyl compounds include styrene, α-methylstyrene, chlorostyrene, and vinyltoluene. Examples of α-olefin compounds include 1-hexene, 1-octene, 1-dodecene and the like.

The above monomers may be used singly or in combination of two or more.

In addition, in order to exhibit the effect of imparting foam stabilizing ability and adhesive strength to difficult-to-adhere substrates in a well-balanced manner, the number of carbon atoms in the hydrophobic group possessed by the polymerizable unsaturated monomer (B) is preferably 2 or more and 22 or less. , 4 or more and 18 or less.

The content of the structural unit B derived from the polymerizable unsaturated monomer (B) is 5% by mass or more and 95% by mass or less when the total mass of the structural unit A and the structural unit B is 100% by mass. If the content of the structural unit B is less than 5% by mass, the foam stabilizing ability of the foam stabilizer deteriorates. On the other hand, if the content of the structural unit B exceeds 95% by mass, the adhesive strength to difficult-to-bond substrates will be insufficient. In order to improve the foam stabilizing ability, the content of the structural unit B is preferably 10% by mass or more. Moreover, in order to increase the adhesive strength to the difficult-to-bond substrate, the content of the structural unit B is preferably 90% by mass or less.

As a general trend, the higher the number of carbon atoms in the hydrophobic group of the polymerizable unsaturated monomer (B) or the higher the amount of the polymerizable unsaturated monomer (B), the higher the foam stabilizing ability. Adhesion is reduced. In addition, since the hydrophobic groups of the polymerizable unsaturated monomer (B) are branched, the hydrophobic groups are more likely to be oriented on the surface, so that the foam stabilizing ability is enhanced, but the adhesive strength is lowered.

(Copolymerizable unsaturated monomer (C))
The copolymer X according to the present invention is a structural unit derived from a copolymerizable unsaturated monomer (C) different from both the copolymerizable unsaturated monomer (A) and the copolymerizable unsaturated monomer (B) described above. It may further contain C.

Here, the larger the amount of the polymerizable unsaturated monomer (A) blended, the better the adhesion to difficult-to-adhere substrates, but the foam stabilizing ability tends to decrease. On the other hand, as the blending amount of the polymerizable unsaturated monomer (B) increases, the foam stabilizing ability improves, but the adhesive strength to the difficult-to-adhere substrate tends to decrease. Thus, there is a trade-off relationship between the polymerizable unsaturated monomer (A) and the polymerizable unsaturated monomer (B). Therefore, in order to eliminate this trade-off, in the present invention, a polymerizable unsaturated monomer (C) may be added to the monomer mixture Mm when synthesizing the copolymer X. In addition, by blending the polymerizable unsaturated monomer (C), it is also possible to improve surface activity (performance to reduce surface tension) and affinity (adhesiveness) with a substrate.

Examples of the copolymerizable unsaturated monomer (C) include, for example, hydroxyl group-containing (meth)acrylates which are monoesterified products of (meth)acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, and glycol (meth)acrylates. acrylamide or methacrylamides, hydrophilic vinyl compounds, carboxyl group-containing polymerizable unsaturated monomers, ether group-containing polymerizable unsaturated monomers, reactive silicones having methacryloyloxy groups, fluorine-containing (meth)acrylate monomers and polyfunctional unsaturated monomers.

Examples of hydroxyl group-containing (meth)acrylates, which are monoesterified products of (meth)acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) ) acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl (meth)acrylate and the like. Examples of glycol (meth)acrylates include methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, and phenoxypropylene glycol (meth)acrylate.

Examples of acrylamides or methacrylamides include acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide butyl ether, N-methylolmethacrylamide butyl ether, N-ethylacrylamide, N-ethylmethacrylamide, Nn - propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-hydroxymethylacrylamide , N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N,N-diethylmethacrylamide , N-methyl, N-ethylacrylamide, N-methyl,N-ethylmethacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminopropylmethacrylamide, N-methylolacrylamide methyl ether, N-methylolmethacrylamide amidomethyl ether, N-methylol acrylamide ethyl ether, N-methylol methacrylamide ethyl ether, N-methylol acrylamide propyl ether, N-methylol methacrylamide propyl ether, acryloylmorpholine, methacryloylmorpholine and the like.

Examples of hydrophilic vinyl compounds include N-vinyl-2-pyrrolidone. Examples of carboxyl group-containing polymerizable unsaturated monomers include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, β-carboxyethyl acrylate and the like. Further, ether group-containing unsaturated monomers (monomers not satisfying general formula (1)) include, for example, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (Meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate and the like.

Commercial products of reactive silicone having a methacryloyloxy group include, for example, Silaplane FM-0711, FM-0721, FM-0725 and TM-0701T manufactured by JNC Corporation, AK-5 and AK- manufactured by Toagosei Co., Ltd. 30, X22-164A, X22-164B and X22-164C manufactured by Shin-Etsu Silicone Co., Ltd.;

Examples of fluorine-containing (meth)acrylate monomers include trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, and tridecafluorooctyl (meth)acrylate.

Examples of polyfunctional unsaturated monomers include divinylbenzene, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, 1,6-hexamethylene glycol di(meth)acrylate. ) acrylate, neopentyl glycol di(meth)acrylate, and the like.

These monomers may be used singly or in combination of two or more.

The content of the structural unit C derived from the polymerizable unsaturated monomer (C) is 50 when the total mass of the polymerizable unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is 100 parts by mass. It is preferably no more than parts by mass. If the content of the structural unit C exceeds 50 parts by mass, it may adversely affect the foam stabilizing ability, the adhesive strength to difficult-to-adhere substrates, the stability of the polyurethane foam, and the like.

(Weight average molecular weight of copolymer X)
The weight average molecular weight Mw of the copolymer X according to the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 500,000, and even more preferably 5,000 to 100,000. When the weight-average molecular weight Mw is within the above range, high foam stabilizing ability can be exhibited while maintaining adhesive strength to difficult-to-adhere substrates at a practical level or higher. From the viewpoint of further enhancing the foam stabilizing ability, the weight average molecular weight is preferably 5,000 or more and 40,000 or less. If the weight average molecular weight Mw exceeds 500,000, although it has a high foam stabilizing ability, poorly dispersed substances (undispersed aggregates) may occur and the effect of the foam stabilizing agent may not be sufficiently exhibited. The molecular weight Mw is preferably 500,000 or less.

In this specification, the weight average molecular weight Mw is a value calculated based on the molecular weight of standard polystyrene from a chromatogram measured by gel permeation chromatography (GPC). In addition, in the measurement of the weight average molecular weight Mw in the examples described later, "HLC8320GPC" (manufactured by Tosoh Corporation, trade name) was used as the GPC measuring instrument, and the columns were "TSKgel GMHxL" x 2, "TSKgel G-2500HxL" and "TSKgel G-2000HxL" (both manufactured by Tosoh Corporation, trade names), using a total of four, using tetrahydrofuran as the mobile phase, using RI as the detector, measuring temperature at 40°C, and flow rate at 1 cc/min. Measurement was performed under the conditions of

(SP value of foam stabilizer)
Further, the solubility parameter (hereinafter referred to as "SP value") of the foam stabilizer according to the present invention is lower than the SP value of polyol, which is a raw material for producing polyurethane foam, and the difference ( SP difference) is preferably in the range of 1.0 or more and 3.1 or less. By setting the SP difference within the range of 1.0 or more and 3.1 or less, while maintaining sufficient adhesive strength of the polyurethane foam to the difficult-to-adhere substrate, the foam stabilizing ability of the foam stabilizer can be adjusted outside the above range. It can be even higher than the case. On the other hand, when the SP difference is less than 1.0 (>0), the foam stabilizer dissolves in the mixed solution of the polyurethane foam raw materials, and the effect of adding the foam stabilizer (foam stabilization ability is sufficiently exhibited. effect) may not be obtained. In addition, when the SP difference exceeds 3.1, the foam stabilizer cannot be finely dispersed in the mixed solution of the polyurethane foam raw materials, and the foam is broken rather than stabilized (acts like an antifoaming agent). tend to From the viewpoint of enhancing the effect of adding the foam stabilizer, the SP difference is more preferably 1.3 or more, and even more preferably 1.5 or more. From the viewpoint of stabilizing bubbles, the SP difference is more preferably 2.9 or less, even more preferably 2.8 or less, and even more preferably 2.0 or less.

In this specification, the SP value of the polyol is the value measured by the turbidity point titration method, and the SP value of the foam stabilizer is the value calculated by the Fedors calculation method.

The SP value by turbidity point titration can be measured by the following method (see SUH, CLARKE, JPSA-1, 5, 1671-1681 (1967)). First, 0.5 g of the polyol or foam stabilizer to be measured for the SP value was weighed into a 100 ml beaker, 10 ml of acetone was added to the beaker using a whole pipette, and the solution dissolved with a magnetic stirrer was used as a sample solution. do. A poor solvent is added dropwise to this sample solution at a measurement temperature of 20° C. using a 50 ml buret, and the drop amount (turbidity point) is defined as the point at which turbidity occurs (turbidity point titration). Regarding the poor solvent, deionized water is used as a poor solvent having a high SP value (hereinafter abbreviated as "high SP poor solvent"), and a poor solvent having a low SP value (hereinafter, "low SP poor solvent" abbreviated as ), and perform turbidity point titration using each poor solvent separately. The SP value δ of the polyol or foam stabilizer is calculated by the following formula (2).
δ=(Vml ^1/2 δml+Vmh ^1/2 δmh)/(Vml ^1/2 +Vmh ^1/2 ) (2)

In the above formula (2), Vml is the molecular volume (= molecular weight / density) of the poor solvent (n-hexane in this specification) at the turbid point when titrated with a low SP poor solvent [mL / mol], δml is the SP value of the poor solvent (n-hexane in this specification) when titrated with a low SP poor solvent, Vmh is the poor solvent at the turbid point when titrated with a high SP poor solvent (here The molecular volume [mL/mol] of the ion-exchanged water) and δmh respectively indicate the SP value of the poor solvent (here, ion-exchanged water) when titrated with a high SP poor solvent.

Vml, Vmh, δml and δmh in formula (2) can be calculated by the following formulas (2a) and (2b) using the titration amount titrated with each poor solvent.
Vm=V1V2/(φ1V2+φ2V1) (2a)
δm=φ1δ1+φ2δ2 (2b)

In the above formulas (2a) and (2b), Vm is Vml or Vmh, δm is δml or δmh, V1 is the molecular volume of the sample solution solvent (acetone in this specification) at the turbid point [mL/mol], V2 is the molecular volume [mL/mol] of the poor solvent (here, ion-exchanged water or n-hexane) at the turbid point, φ1 is the volume fraction of the sample solution solvent (here, acetone) at the turbid point, φ2 indicates the volume fraction of the poor solvent (in this specification, ion-exchanged water or n-hexane) at the turbid point.

In addition, in the examples described later, the SP value of the polyol was measured by the turbidity point titration method described above.

Also, the SP value by the Fedors calculation method is F. It can be calculated by the calculation method described in "Polymer Engineering and Science" by Fedors, 14(2), 147 (1974). In the Fedors calculation method, the SP value is calculated based on the cohesive energy and molecular volume of the substituent (atom or atomic group) of the target compound.

In the examples described later, the SP values of the foam stabilizers in Synthesis Examples and Comparative Synthesis Examples were calculated by this Fedors calculation method.

(Use of foam stabilizer)
The use of the foam stabilizer according to the present invention is not particularly limited as long as it is used as a foam stabilizer for controlling the foam volume, cell diameter, etc. of a foam in the production of polyurethane foam. However, it can be particularly suitably used as a foam stabilizer for rigid polyurethane foams.

[Method for producing foam stabilizer]
The method for producing a foam stabilizer for polyurethane foam according to the present invention described above includes a polymerization step of obtaining the copolymer X described above. In the polymerization step, the copolymer X is a monomer mixture containing 5 to 95% by mass of the above polymerizable unsaturated monomer (A) and 5 to 95% by mass of the above polymerizable unsaturated monomer (B). It is synthesized by copolymerizing Mm. A predetermined amount of the polymerizable unsaturated monomer (C) described above may be added to the monomer mixture Mm used for synthesizing the copolymer X, if necessary.

(Polymerization method)
The method for synthesizing the copolymer X according to the present invention is not particularly limited, and known methods such as a solution polymerization method, a dispersion polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, and a living radical polymerization method. A polymerization method is used. As the polymerization initiator, known azo polymerization initiators, peroxides and the like can be used, and an appropriate initiator may be used depending on the type of polymerization reaction.

(Addition amount of polymerizable unsaturated monomer (A))
The blending amount of the polymerizable unsaturated monomer (A) is 5% by mass or more and 95% by mass or less when the total mass of the polymerizable unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is 100% by mass. is. If the content of the polymerizable unsaturated monomer (A) is less than 5% by mass, the adhesive strength to difficult-to-adhere substrates will be insufficient. On the other hand, when the blending amount of the polymerizable unsaturated monomer (A) exceeds 95% by mass, the foam stabilizing ability of the foam stabilizing agent deteriorates. In order to increase the adhesive strength to the difficult-to-adhere substrate, the blending amount of the polymerizable unsaturated monomer (A) is preferably 10% by mass or more. Moreover, in order to improve the foam stabilizing ability, the blending amount of the polymerizable unsaturated monomer (A) is preferably 90% by mass or less.

(Addition amount of polymerizable unsaturated monomer (B))
Further, the blending amount of the polymerizable unsaturated monomer (B) is 5% by mass or more and 95% by mass when the total mass of the polymerizable unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is 100% by mass. % or less. If the blending amount of the polymerizable unsaturated monomer (B) is less than 5% by mass, the foam stabilizing ability of the foam stabilizing agent is deteriorated. On the other hand, if the blending amount of the polymerizable unsaturated monomer (B) exceeds 95% by mass, the adhesive strength to difficult-to-adhere substrates will be insufficient. In order to improve the foam stabilizing ability, the blending amount of the polymerizable unsaturated monomer (B) is preferably 10% by mass or more. Moreover, in order to increase the adhesive strength to the difficult-to-adhere substrate, the blending amount of the polymerizable unsaturated monomer (B) is preferably 90% by mass or less.

(Additional amount of polymerizable unsaturated monomer (C))
Furthermore, the blending amount of the polymerizable unsaturated monomer (C) is 50 parts by mass or less when the total mass of the polymerizable unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is 100 parts by mass. is preferred. If the blending amount of the polymerizable unsaturated monomer (C) exceeds 50 parts by mass, it may adversely affect the foam stabilizing ability, the adhesive strength to difficult-to-adhere substrates, the stability of the polyurethane foam, and the like.

[Polyurethane foam]
The polyurethane foam according to the present invention is a foam obtained by foaming and curing a urethane raw material mixture Mu (mixed solution as a polyurethane foam raw material) containing a polyisocyanate, a polyol, and the foam stabilizer for polyurethane foam described above. is. Polyurethane foams according to the present invention include all rigid polyurethane foams, flexible polyurethane foams and semi-rigid polyurethane foams.

Of these, rigid polyurethane foam has an excellent feature of self-adhesion that is not found in other heat insulating materials. This is due to the property that a layer strongly adhered to the object can be formed by directly foaming the mixed solution on the surface of the object such as metal, plywood, concrete, resin, etc., without using an adhesive. be. Using this property, the surface of the object (substrate) such as a composite panel, laminate board, etc. can be cured simply by applying the mixed solution to the object by spraying and foaming and curing the mixed solution on the surface of various objects. Polyurethane foam laminates can be produced in which polyurethane foam is laminated to If the surface of the object (base material) is previously coated with a primer or the like, the polyurethane foam can be adhered to the surface of the object more strongly.

(Content of foam stabilizer)
The content of the foam stabilizer according to the present invention is preferably 0.1% by mass or more and 5.0% by mass or less in the urethane raw material mixture Mu (mixed solution as a polyurethane foam raw material). If the content of the foam stabilizer is less than 0.1% by mass, the foam stabilizing ability may deteriorate. On the other hand, if the content of the foam stabilizer exceeds 5.0% by mass, the mechanical properties of the polyurethane foam may deteriorate, and it may cause stickiness and contamination. From the viewpoint of increasing the foam stabilizing ability, the content of the foam stabilizer is more preferably 0.3% by mass or more, further preferably 0.7% by mass or more, and 1.5% by mass or more. It is even more preferred to have In addition, from the viewpoint of increasing adhesive strength, the content of the foam stabilizer is more preferably 2.5% by mass or less, further preferably 1.5% by mass or less, and 0.7% by mass or less. is even more preferable.

(SP value of foam stabilizer)
As described above, the SP value of the foam stabilizer according to the present invention is 1.0 to 3.1 lower than the SP value of the polyol that is the raw material for producing the polyurethane foam, that is, the SP value of the polyol It is preferably low and the difference (SP difference) is in the range of 1.0 or more and 3.1 or less.

(Uses of polyurethane foam)
INDUSTRIAL APPLICABILITY The polyurethane foam of the present invention can be suitably used as a building material, a ship for oil and gas transportation, and a heat retaining material, a heat insulating material, etc. in electric appliances such as a refrigerator. In particular, in reinforced concrete buildings, etc., it can be used as a foam for the spraying method because it is easy to perform insulation work.

[Method for producing polyurethane foam]
The method for producing a polyurethane foam according to the present invention described above includes a foam stabilizer mixing step and a foam producing step.

(Foam stabilizer mixing step)
In the foam stabilizer mixing step, the polyol and the foam stabilizer for polyurethane foam described above are mixed to obtain a polyol mixture Mo. In addition to the polyol and the foam stabilizer, the polyol mixture Mo of the present invention may contain a foaming agent, a catalyst, other additives, and the like. As a method for mixing each raw material in the polyol mixture Mo, a known method can be used. For example, each raw material can be mixed by stirring using a disper. Each component in the polyol mixture Mo will be described in detail below.

(polyol)
Polyols are incorporated as curing agents in the production of polyurethane foams according to the present invention. The polyol used in the method for producing the polyurethane foam of the present invention is not particularly limited as long as it is generally used for the production of polyurethane foam. Examples include polyester polyol, polyether polyol, polyether ester polyol, and polylactone polyol. , polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polymer polyols, and the like. Among these, polyester polyols and polyether polyols are suitable as the polyols of the present invention.

Polyester polyols include, for example, polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and ring-opening polymerization of lactones such as ε-caprolactone, α-methyl-ε-caprolactone and methylvalerolactone. and condensates of hydroxycarboxylic acids and the above polyhydric alcohols. Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, malonic acid, succinic acid, and naphthalenedicarboxylic acid. Polyhydric alcohols used in the synthesis of polyester polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, octanediol, nonanediol, bisphenol A, and the like. is mentioned. Furthermore, hydroxycarboxylic acids include, for example, castor oil, reaction products of castor oil and ethylene glycol, and the like.

Examples of polyether polyols include alkylene oxide adducts of polyhydric alcohols. Examples of polyhydric alcohols used in the synthesis of polyether polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and the like. . Moreover, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Examples of polyether ester polyols include those obtained by reacting the above-described polyether polyols with polybasic acids to esterify them, and those having both polyether and polyester segments in one molecule.

Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Polycarbonate polyols are obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol and nonanediol with diethylene carbonate, dipropylene carbonate and the like. polyols and the like.

Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolak, and cresol novolak. Alicyclic polyols include, for example, cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Furthermore, examples of aliphatic polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and the like.

These polyols may be used singly or in combination of two or more. Moreover, the hydroxyl value of these polyols is preferably 10 to 600 mgKOH/g, more preferably 30 to 500 mgKOH/g. The hydroxyl value in the present invention is a value measured according to JIS-K0070.

The blending amount of polyol is preferably 20 to 80% by mass when the total amount of polyurethane foam raw materials is taken as 100% by mass.

(foam stabilizer)
As described above, the foam stabilizer according to the present invention is blended in order to increase the compatibility of each component (polyisocyanate, polyol, etc.) of the polyurethane raw material and to reduce the surface tension of the mixed solution of the polyurethane raw material. As a result, the gas involved in the mixed solution can be easily dispersed, so that the cells in the foam can be made uniform and stabilized, and the cell structure (foam volume, cell diameter, etc.) can be adjusted. This cell structure has a great influence on the physical properties of the polyurethane foam. As such a foam stabilizer, the polyurethane foam foam stabilizer described above is used in the present invention.

The blending amount of the foam stabilizer according to the present invention is preferably 0.1% by mass or more and 5.0% by mass or less in the urethane raw material mixture Mu (mixed solution as a polyurethane foam raw material). If the amount of the foam stabilizer is less than 0.1% by mass, the foam-stabilizing ability may be lowered. On the other hand, if the amount of the foam stabilizer exceeds 5.0% by mass, the mechanical properties of the polyurethane foam may be lowered, and stickiness and contamination may be caused. From the viewpoint of enhancing the foam stabilizing ability, the amount of the foam stabilizer is more preferably 0.3% by mass or more, further preferably 0.7% by mass or more, and more preferably 1.5% by mass or more. It is even more preferred to have In addition, from the viewpoint of increasing the adhesive strength, the amount of the foam stabilizer is more preferably 2.5% by mass or less, further preferably 1.5% by mass or less, and 0.7% by mass or less. is even more preferable.

(foaming agent)
The foaming agent improves the foaming action when the polyisocyanate (first liquid) and other components (second liquid) are mixed to form a foam (polyurethane foam). Specifically, it is blended to promote foaming of the urethane resin.

Examples of foaming agents include organic physical foaming agents such as water, hydrocarbons, chlorinated aliphatic hydrocarbons, fluorine compounds, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, ethers, or mixtures thereof, or , nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. One of these foaming agents may be used alone, or two or more thereof may be used in combination.

Examples of the hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of chlorinated aliphatic hydrocarbons include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Examples of fluorine compounds include CHF ₃ , CH ₂ F ₂ , CH ₃ F and the like. Hydrochlorofluorocarbons include, for example, trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1 -chloro-1,1-difluoroethane)) and the like. Examples of hydrofluorocarbons include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of hydrofluoroolefins include HFO-1233zd ((E)-1-chloro-3,3,3-trifluoropropene). Ethers include, for example, diisopropyl ether and the like.

The blending amount of the foaming agent is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyol.

(catalyst)
The catalyst used in the method for producing a polyurethane foam according to the present invention mainly includes a trimerization catalyst. Moreover, you may use a foaming catalyst and a resin-forming catalyst as a catalyst.

<Trimerization catalyst>
The trimerization catalyst is blended in order to react and trimerize the isocyanate groups contained in the polyisocyanate described later, thereby promoting the formation of isocyanurate rings. Known trimerization catalysts can be used, for example, tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S - Nitrogen-containing aromatic compounds such as triazine, carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, tertiary ammonium salts such as trimethylammonium salts, triethylammonium salts and triphenylammonium salts, Examples include quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts, tetraphenylammonium salts and the like.

The blending amount of the trimerization catalyst is preferably 0.5 to 20% by mass when the total of the raw materials for the polyurethane foam is 100% by mass.

<Foaming catalyst>
A foaming catalyst accelerates the reaction between polyisocyanate and water. Specifically, it is blended to promote foaming of the mixed solution of the polyurethane foam raw materials by the carbon dioxide generated by the reaction of the polyisocyanate and water. As the foaming catalyst, a known one can be used. acid-block type catalysts in which the substance is neutralized with carboxylic acid;

The blending amount of the foaming catalyst is preferably 0.1 to 10% by mass when the total amount of the raw materials for the polyurethane foam is 100% by mass.

<Resin catalyst>
A resinification catalyst (metal catalyst) is added to promote the reaction between polyisocyanate and polyol. A known resinification catalyst can be used, and examples thereof include metal salts of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like. Among these, organic acid metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like are suitable as the resinification catalyst.

The blending amount of the resinification catalyst is preferably 0.1 to 10% by mass when the total of the raw materials for the polyurethane foam is 100% by mass.

(Other additives)
The polyol mixture Mo of the present invention contains flame retardants, dispersants, cross-linking agents, chain extenders, fillers, dyes, pigments, antioxidants, ultraviolet absorbers, antibacterial agents, etc., as long as they do not impair the effects of the present invention. known additives may be blended.

A flame retardant is added to impart flame retardancy to the polyurethane foam according to the present invention. However, in the present invention, red phosphorus is not included as a flame retardant. When red phosphorus is used as the raw material for the polyurethane foam of the present invention, sufficient adhesion to hard-to-bond substrates cannot be obtained. The inventors consider the reason as follows. Red phosphorus reacts with water to produce phosphoric acid. The generated phosphoric acid corrodes the polyurethane resin and may open holes up to the surface of the resin. In this case, the mechanical strength of the polyurethane foam is lowered. As a result, there is a possibility of causing a decrease in adhesion of the polyurethane foam to the substrate. Therefore, the present invention does not contain red phosphorus as a flame retardant in order to obtain sufficient adhesive strength to hard-to-adhere substrates.

A dispersant is added to improve the dispersibility of additives such as flame retardants in the mixed solution of polyurethane foam raw materials. Moreover, the cross-linking agent is added to adjust the hardness of the polyurethane foam.

(Foam generation process)
In the foam production step, the polyol mixture Mo obtained in the foam stabilizer mixing step and the polyisocyanate are foamed and cured while being mixed to obtain a polyurethane foam. A known method can be used as a method for mixing the polyol mixture Mo and the polyisocyanate and a method for foaming the polyol mixture Mo and the polyisocyanate in the foam generation step. , foaming and resin curing reactions proceed. The polyisocyanates that can be used in the present invention are described in detail below.

(polyisocyanate)
Polyisocyanate is blended as a main ingredient in the production of the polyurethane foam according to the present invention. The polyisocyanate used in the method for producing the polyurethane foam of the present invention is not particularly limited as long as it is generally used for the production of polyurethane foam. isocyanate and the like.

Here, examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate. .

In addition, examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like.

Further, examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.

These polyisocyanates may be used singly or in combination of two or more.

Here, the isocyanate index of the polyurethane foam used in the present invention is preferably 100-600. The isocyanate index is used as an index indicating the mixing ratio of polyol and polyisocyanate, and is obtained by dividing the number of moles of isocyanate groups (NCO) in polyisocyanate by the total number of moles of all active hydrogen groups in the polyurethane foam raw material. It is a value obtained by multiplying the value by 100, and is calculated by [(NCO equivalent in polyurethane foam raw material/equivalent of active hydrogen in polyurethane foam raw material)×100].

The blending amount of polyisocyanate is preferably 20 to 80% by mass when the total amount of polyurethane foam raw materials is taken as 100% by mass.

[Polyurethane foam laminate]
The polyurethane foam laminate according to the present invention is a laminate in which the polyurethane foam described above is laminated on the surface of a substrate. The substrate on which the polyurethane foam of the present invention is laminated is a substrate selected from the group consisting of polypropylene resin, polyethylene resin, fluororesin and silicone resin, or a difficult-to-adhere substrate such as a substrate coated with wax. . The term "difficult-to-adhere base material" refers to a base material that is difficult to bond with a polyurethane foam using the self-adhesiveness of a rigid polyurethane foam or with a general adhesive, as described above. . The "wax" in the present invention is not particularly limited, and known waxes such as waxes, paraffin waxes, and lustering agents containing microwax as a main component can be used, for example.

Here, generally, a silicone-based foam stabilizer is used as a foam stabilizer for producing polyurethane foam. According to the studies by the present inventors, it is believed that the reason why the polyurethane foam does not have sufficient adhesion to the above-mentioned difficult-to-adhere substrate is due to the use of the silicone-based foam stabilizer. The reason for this is presumed by the present inventors as follows. There is the concept of adhesion work, which indicates the work of separating

objects

1 and 2 that are in contact with each other at the interface. Assuming that the surface free energies of Object 1 and Object 2 are _γ1 and _γ2 , respectively, and the interfacial free energy at the interface between Object 1 and Object 2 is _γ12 , the work of adhesion Wa is expressed by the following equation, is called the duple formula.
Wa = γ ₁ + γ _{2 -} γ ₁₂

From this Dupre's formula, the higher the surface free energies γ ₁ and γ ₂ of each object, the greater the work of adhesion Wa, and the more difficult it is to separate the objects 1 and 2 (the higher the adhesive strength). Since the silicone-based foam stabilizer lowers the surface free energy of the polyurethane foam, the work of adhesion Wa is reduced. As a result, sufficient adhesive strength to difficult-to-bond substrates cannot be obtained.

Therefore, in the present invention, without using a silicone-based foam stabilizer as a foam stabilizer, the ether group-containing polymerizable unsaturated monomer (A) as described above and a polymerizable unsaturated monomer having a hydrophobic group ( A copolymer X obtained by copolymerizing a monomer mixture Mm containing B) is used as a foam stabilizer. As a result, it is possible to obtain a foam stabilizer for polyurethane foam having a foam stabilizing ability equal to or higher than that of a silicone-based foam stabilizer, and to provide polyurethane foam with sufficient adhesion even to the above-described difficult-to-adhere substrates. It becomes possible to The reason for this is presumed by the present inventors as follows. That is, the foam stabilizer according to the present invention can exhibit foam-stabilizing ability without lowering the surface free energy of the polyurethane foam as much as the silicone-based foam stabilizer. Therefore, the polyurethane foam obtained using the foam stabilizer according to the present invention has a larger work of adhesion Wa than when a silicone-based foam stabilizer is used, and thus has sufficient adhesion even to a difficult-to-bond substrate. Forces can be imparted to polyurethane foam.

[Method for manufacturing polyurethane foam laminate]
The method for producing a polyurethane foam laminate according to the present invention comprises a substrate selected from the group consisting of polypropylene resin, polyethylene resin, fluororesin and silicone resin, or a wax-coated substrate (difficult-to-bond substrate); It includes a lamination step of laminating polyurethane foam, which is a foam obtained by the manufacturing method described above. In the method for producing a polyurethane foam laminate of the present invention, a mixed solution of polyurethane foam raw materials is applied to a substrate, and foamed and cured directly on the surface of the substrate to laminate a layer of polyurethane foam on the surface of the substrate. It includes not only the case of forming a polyurethane foam, but also the case of adhering the produced polyurethane foam to a base material using an adhesive or the like after preparing the polyurethane foam in advance. In the former case, the self-adhesiveness of rigid polyurethane foam is mainly used to adhere the polyurethane foam to the substrate.

When using the self-adhesiveness of rigid polyurethane foam to bond polyurethane foam to a base material, a mixed solution of polyurethane foam raw materials is applied to the target base material by spraying or the like, and the mixed solution is applied to the surface of the base material. It is possible to produce a polyurethane foam laminate in which polyurethane foam is laminated to the surface of an object such as a composite panel, laminate board, etc., simply by foaming and curing the . In this case, the polyol mixture Mo and the polyisocyanate can be mixed in advance in a spraying device such as a sprayer immediately before the application of the polyurethane foam raw material (construction of the foam).

If the surface of the object (base material) is previously coated with a primer, etc., it becomes possible to bond the polyurethane foam to the surface of the object more strongly.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments. That is, it is understood that other forms or various modifications that can be conceived by those skilled in the art within the scope of the invention described in the claims also belong to the technical scope of the present invention.

The present invention will be specifically described below with reference to examples. It should be noted that the present invention is in no way restricted to these examples. Also, "%" and "parts" in the examples indicate "% by mass" and "parts by mass" unless otherwise specified.

[Synthesis of foam stabilizer]
First, foam stabilizers of Synthesis Examples 1 to 60 and Foam Stabilizer Comparative Examples 1 and 2 were synthesized as follows. As foam stabilizer comparative examples 3 and 4, commercially available silicone foam stabilizers were prepared. Details of the method for synthesizing the foam stabilizer and commercially available products are described below.

(Synthesis example 1)
200.0 parts of propylene glycol monomethyl ether as solvent (a-1) was charged into a 1000 ml reaction vessel equipped with a stirrer, reflux condenser, dropping pump and vessel, as well as a thermometer and a nitrogen gas inlet tube. After that, the internal temperature was raised to 100° C. while stirring under a nitrogen gas stream. 237.5 parts of ethyl acrylate, 12.5 parts of methoxypolyethylene glycol methacrylate (trade name: NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), and 100 parts of propylene glycol monomethyl ether were added to the dropping container as the dropping solution (b-1). A mixture of 0 parts and 40.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate was charged. Next, while maintaining the internal temperature of the reaction vessel at 100° C., the dropping solution (b-1) was uniformly dropped over 90 minutes. After the dropwise addition was completed, the reaction temperature was maintained at 100°C for 60 minutes, then 3.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate was added, and the reaction was continued at 100°C for 120 minutes. gone. After completion of the reaction, the solvent was removed by an evaporator to obtain a copolymer as a foam stabilizer in Synthesis Example 1. The synthesized copolymer had a weight average molecular weight of 2700 and an SP value of 10.2.

(Synthesis example 2)
175.0 parts of ethyl acrylate, 62.5 parts of dibutyl fumarate, methoxy polyethylene glycol methacrylate (trade name NK Ester M-40G: Shin-Nakamura Chemical Co., Ltd.) 12.5 parts, 100.0 parts of propylene glycol monomethyl ether and 45.0 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution, and the reaction temperature during dropping was A copolymer as a foam stabilizer in Synthesis Example 2 was obtained in the same manner as in Synthesis Example 1, except that the temperature was set to 125°C. The synthesized copolymer had a weight average molecular weight of 1900 and an SP value of 10.1.

(Synthesis Example 3)
212.5 parts of ethyl acrylate as a dropping solution (b-3) instead of the dropping solution (b-1) of Synthesis Example 1, methoxy polyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 37 .5 parts, 50.0 parts of propylene glycol monomethyl ether, and 10.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate. to obtain a copolymer as a foam stabilizer. The synthesized copolymer had a weight average molecular weight of 13,500 and an SP value of 10.1.

(Synthesis Example 4)
Using 200 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and isostearyl acrylate 12 as a dropping solution (b-4) instead of the dropping solution (b-1) .5 parts, 237.5 parts of methoxypolyethylene glycol methacrylate (trade name: NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 50.0 parts of butyl acetate and 50 parts of tertiary-amylperoxy-2-ethylhexanoate % solution was used in the same manner as in Synthesis Example 1 to obtain a copolymer as a foam stabilizer in Synthesis Example 4. The synthesized copolymer had a weight average molecular weight of 246,100 and an SP value of 9.5.

(Synthesis Example 5)
Using 150 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and 2-ethylhexyl acrylate as the dropping solution (b-5) instead of the dropping solution (b-1). 60.0 parts, methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 120.0 parts, methoxy polyethylene glycol methacrylate (trade name NK Ester M-450G: manufactured by Shin-Nakamura Chemical Co., Ltd.) 20.0 parts, 100.0 parts of butyl acetate and 4.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 120 ° C. Synthesis A copolymer as a foam stabilizer in Synthesis Example 5 was obtained in the same manner as in Example 1. The synthesized copolymer had a weight average molecular weight of 14,300 and an SP value of 9.4.

(Synthesis Example 6)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, dropping solution (b-6) instead of dropping solution (b-1) 2,2- Vinyl dimethyloctanoate (trade name VEOVA 10: manufactured by HEXON) 87.5 parts, methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation) 162.5 parts, butyl acetate 50.0 parts and tertiary -Amylperoxy-2-ethylhexanoate 50% solution 5.0 parts was used, and the foam stabilization of Synthesis Example 6 was performed in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130 ° C. A copolymer was obtained as an agent. The synthesized copolymer had a weight average molecular weight of 12000 and an SP value of 9.4.

(Synthesis Example 7)
Using 120 parts of butyl acetate as solvent (a-2) instead of solvent (a-1) in Synthesis Example 1, and adding 25 parts of butyl acrylate as dropping solution (b-7) instead of dropping solution (b-1). 0 parts, silicone-modified methacrylate (trade name: Silaplane TM-0701T: manufactured by JNC Co., Ltd.) 25.0 parts, methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation) 200.0 parts, butyl acetate 50.0 parts and 6.5 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 130 ° C., in the same manner as in Synthesis Example 1. , to obtain a copolymer as a foam stabilizer in Synthesis Example 7. The synthesized copolymer had a weight average molecular weight of 11,000 and an SP value of 9.4.

(Synthesis Example 8)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-8) instead of the dropping solution (b-1) 75.0 parts, 25.0 parts of styrene, 150.0 parts of methoxypolyethylene glycol acrylate (trade name Blenmar AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and tertiary - amylperoxy -2- The copolymer as a foam stabilizer of Synthesis Example 8 was prepared in the same manner as in Synthesis Example 1, except that 5.0 parts of a 50% solution of ethylhexanoate was used and the reaction temperature during dropping was set to 130°C. Obtained. The synthesized copolymer had a weight average molecular weight of 11,100 and an SP value of 9.6.

(Synthesis Example 9)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-9) instead of the dropping solution (b-1) 75.0 parts, 12.5 parts of acrylic acid, 162.5 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and tertiary-amylperoxy-2 - Copolymer as a foam stabilizer of Synthesis Example 9 in the same manner as in Synthesis Example 1 except that 5.0 parts of a 50% solution of ethylhexanoate was used and the reaction temperature during dropping was set to 130 ° C. got The synthesized copolymer had a weight average molecular weight of 11,200 and an SP value of 9.6.

(Synthesis Example 10)
120 parts of butyl acetate was used as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and 100 parts of isobutyl acrylate was used as the dropping solution (b-10) instead of the dropping solution (b-1). 0 parts, 12.5 parts of 2-hydroxyethyl methacrylate, 137.5 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and tertiary - amyl peroxy - Copolymerization as a foam stabilizer in Synthesis Example 10 was carried out in the same manner as in Synthesis Example 1 except that 5.0 parts of a 50% solution of 2-ethylhexanoate was used and the reaction temperature during dropping was set to 130 ° C. got a union. The weight average molecular weight of the synthesized copolymer was 16000 and the SP value was 9.6.

(Synthesis Example 11)
Using 250 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-11) instead of the dropping solution (b-1) 60.0 parts, polyethylene glycol diacrylate (trade name Miramar M280: manufactured by MIWON) 70.0 parts, methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation) 70.0 parts, butyl acetate 83.0 parts. 3 parts and 10.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 130 ° C. Synthesis was performed in the same manner as in Synthesis Example 1. A copolymer as a foam stabilizer of Example 11 was obtained. The synthesized copolymer had a weight average molecular weight of 21,500 and an SP value of 9.7.

(Synthesis Example 12)
30.0 parts of ethyl acrylate as a dropping solution (b-12) instead of the dropping solution (b-1) of Synthesis Example 1, stearoxy polyethylene glycol methacrylate (trade name Blenmer PSE-1300: manufactured by NOF Corporation)70. 0 parts, 200.0 parts of propylene glycol monomethyl ether, and 6.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used. to obtain a copolymer as a foam stabilizer. The synthesized copolymer had a weight average molecular weight of 15,500 and an SP value of 9.4.

(Synthesis Example 13)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-13) instead of the dropping solution (b-1) 50.0 parts, 25.0 parts of isobutyl vinyl ether, 175.0 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and tertiary-amylperoxy-2 - A copolymer as a foam stabilizer of Synthesis Example 13 was obtained in the same manner as in Synthesis Example 1, except that 2.0 parts of a 50% solution of ethylhexanoate was used. The weight average molecular weight of the synthesized copolymer was 9600 and the SP value was 9.4.

(Synthesis Example 14)
120 parts of butyl acetate was used as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and 222 parts of butyl acrylate was used as the dropping solution (b-14) instead of the dropping solution (b-1). 84 parts, 148.56 parts of methoxypolyethylene glycol acrylate (trade name NK Ester AM-230G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of butyl acetate and 50% tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 14 was obtained in the same manner as in Synthesis Example 1 except that 5.6 parts of the solution was used and the reaction temperature during dropping was set to 110°C. The synthesized copolymer had a weight average molecular weight of 68,100 and an SP value of 9.7.

(Synthesis Example 15)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-15) instead of the dropping solution (b-1) 148.56 parts, 222.84 parts of methoxypolyethylene glycol acrylate (trade name NK Ester AM-230G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 120.0 parts of butyl acetate and tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 15 was obtained in the same manner as in Synthesis Example 1 except that 3.7 parts of a 50% solution was used and the reaction temperature during dropping was set to 110°C. The synthesized copolymer had a weight average molecular weight of 19200 and an SP value of 9.4.

(Synthesis Example 16)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 176 parts of lauryl methacrylate as the dropping solution (b-16) instead of the dropping solution (b-1). 0 parts, 264.0 parts of methoxypolyethylene glycol methacrylate (trade name Miramar M193: manufactured by MIWON), 50.0 parts of butyl acetate and 6.6 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution. A copolymer as a foam stabilizer of Synthesis Example 16 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 125°C. The synthesized copolymer had a weight average molecular weight of 35,100 and an SP value of 9.3.

(Synthesis Example 17)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 132 parts of lauryl acrylate as the dropping solution (b-17) instead of the dropping solution (b-1). 0 parts, 308.0 parts of methoxypolyethylene glycol acrylate (trade name NK Ester AM-130G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 50.0 parts of butyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 17 was obtained in the same manner as in Synthesis Example 1 except that 6.6 parts of the solution was used and the reaction temperature during dropping was set to 125°C. The synthesized copolymer had a weight average molecular weight of 14400 and an SP value of 9.4.

(Synthesis Example 18)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 132 parts of lauryl methacrylate as the dropping solution (b-18) instead of the dropping solution (b-1). 0 parts, 308.0 parts of methoxypolyethylene glycol acrylate (trade name NK Ester AM-130G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 50.0 parts of butyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 18 was obtained in the same manner as in Synthesis Example 1 except that 6.6 parts of the solution was used and the reaction temperature during dropping was set to 125°C. The synthesized copolymer had a weight average molecular weight of 16,100 and an SP value of 9.4.

(Synthesis Example 19)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 132 parts of lauryl methacrylate as the dropping solution (b-19) instead of the dropping solution (b-1). 0 parts, 308.0 parts of methoxypolyethylene glycol methacrylate (trade name Miramar M193: manufactured by MIWON), 50.0 parts of butyl acetate and 6.6 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution. A copolymer as a foam stabilizer of Synthesis Example 19 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 125°C. The synthesized copolymer had a weight average molecular weight of 32,300 and an SP value of 9.3.

(Synthesis Example 20)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and isostearyl acrylate 87 as a dropping solution (b-20) instead of the dropping solution (b-1) .9 parts, 205.1 parts of methoxypolyethylene glycol acrylate (trade name: Blenmar AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and tertiary-amylperoxy-2-ethylhexanoate 50% solution A copolymer as a foam stabilizer of Synthesis Example 20 was obtained in the same manner as in Synthesis Example 1 except that 20.0 parts of the copolymer was used and the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 6300 and an SP value of 9.0.

(Synthesis Example 21)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and isostearyl acrylate 58 as a dropping solution (b-21) instead of the dropping solution (b-1) .6 parts, 234.4 parts of methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and 50% solution of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 21 was obtained in the same manner as in Synthesis Example 1, except that 1.5 parts was used and the reaction temperature during dropping was set to 130°C. The weight average molecular weight of the synthesized copolymer was 10400 and the SP value was 9.2.

(Synthesis Example 22)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and isostearyl acrylate 29 as a dropping solution (b-22) instead of the dropping solution (b-1). .3 parts, 263.7 parts of methoxypolyethylene glycol acrylate (trade name: Blenmer AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and 50% solution of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 22 was obtained in the same manner as in Synthesis Example 1, except that 1.5 parts of the copolymer was used and the reaction temperature during dropping was set to 110°C. The synthesized copolymer had a weight average molecular weight of 15,500 and an SP value of 9.4.

(Synthesis Example 23)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 50 parts of isostearyl acrylate as a dropping solution (b-23) instead of the dropping solution (b-1). .0 parts, 100.0 parts of methoxyethyl acrylate (trade name: 2-MTA: manufactured by Osaka Organic Chemical Industry Co., Ltd.), 100.0 parts of methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation), The procedure of Synthesis Example 1 was repeated except that 50.0 parts of butyl acetate and 5.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 130°C. A copolymer as a foam stabilizer of Synthesis Example 23 was obtained by the method. The synthesized copolymer had a weight average molecular weight of 12,100 and an SP value of 9.4.

(Synthesis Example 24)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and isostearyl acrylate 42 as a dropping solution (b-24) instead of the dropping solution (b-1) .1 part, 42.1 parts of isobornyl methacrylate, 198.8 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 50.0 parts of butyl acetate and tertiary-amylperoxy- Copolymerization as a foam stabilizer in Synthesis Example 24 was carried out in the same manner as in Synthesis Example 1 except that 4.0 parts of a 50% solution of 2-ethylhexanoate was used and the reaction temperature during dropping was set to 130 ° C. got a union. The synthesized copolymer had a weight average molecular weight of 9500 and an SP value of 9.3.

(Synthesis Example 25)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, dropping solution (b-25) instead of dropping solution (b-1) C18-24 alkyl Methacrylate (Blenmer VMA-70: manufactured by NOF Corporation) 29.3 parts, methoxy polyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation) 263.7 parts, butyl acetate 200.0 parts and tertiary -Amylperoxy-2-ethylhexanoate 50% solution 6.7 parts was used, and the foam stabilization of Synthesis Example 25 was performed in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130 ° C. A copolymer was obtained as an agent. The synthesized copolymer had a weight average molecular weight of 9200 and an SP value of 9.2.

(Synthesis Example 26)
Using 400 parts of isobutyl acetate as a solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and adding 46.5 parts of lauryl methacrylate as a dropping solution (b-26) instead of the dropping solution (b-1). 9 parts, 109.4 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of isobutyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 26 was obtained in the same manner as in Synthesis Example 1, except that 0.2 part of the solution was used and the reaction temperature during dropping was set to 85°C. The synthesized copolymer had a weight average molecular weight of 365,200 and an SP value of 9.4.

(Synthesis Example 27)
Using 400 parts of isobutyl acetate as the solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and adding 46.5 parts of lauryl methacrylate as the dropping solution (b-27) instead of the dropping solution (b-1). 9 parts, 109.4 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of isobutyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate Same as Synthesis Example 1 except that 0.2 part of the solution was used, the reaction temperature during dropping was set to 85° C., and no additional tertiary-amylperoxy-2-ethylhexanoate 50% solution was added. A copolymer as a foam stabilizer of Synthesis Example 27 was obtained by the method of. The synthesized copolymer had a weight average molecular weight of 590,700 and an SP value of 9.4.

(Synthesis Example 28)
Using 150 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 40 parts of lauryl methacrylate as the dropping solution (b-28) instead of the dropping solution (b-1). 0 parts, 360.0 parts of methoxypolyethylene glycol methacrylate (trade name Miramar M193: manufactured by MIWON), 50.0 parts of butyl acetate and 6.0 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution. A copolymer as a foam stabilizer of Synthesis Example 28 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 17700 and an SP value of 9.3.

(Synthesis Example 29)
Using 150 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-29) instead of the dropping solution (b-1) 75.0 parts, tetrahydrofurfuryl acrylate (trade name: Viscoat #150: manufactured by Osaka Organic Chemical Industry Co., Ltd.) 25.0 parts, methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation) 150.0 parts Parts, 50.0 parts of butyl acetate and 6.0 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution were used, and the reaction temperature during dropping was set to 130 ° C., except that Synthesis Example 1 and A copolymer as a foam stabilizer of Synthesis Example 29 was obtained in the same manner. The synthesized copolymer had a weight average molecular weight of 10,300 and an SP value of 9.3.

(Synthesis Example 30)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-30) instead of the dropping solution (b-1) 75.0 parts, dimethylaminoethyl methacrylate (trade name Acryester DM: manufactured by Mitsubishi Chemical Corporation) 25.0 parts, methoxypolyethylene glycol acrylate (trade name Blemmer AME-400: manufactured by NOF Corporation) 150.0 parts, The procedure of Synthesis Example 1 was repeated except that 50.0 parts of butyl acetate and 6.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 130°C. A copolymer as a foam stabilizer of Synthesis Example 30 was obtained by the method. Due to the presence of cationic groups, the weight average molecular weight of the synthesized copolymer could not be measured. Moreover, the SP value of the synthesized copolymer was 9.2.

(Synthesis Example 31)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-31) instead of the dropping solution (b-1) 75.0 parts, acryloyl morpholine (trade name ACMO: manufactured by KJ Chemicals Co., Ltd.) 25.0 parts, methoxypolyethylene glycol acrylate (trade name Blemmer AME-400: manufactured by NOF Corporation) 150.0 parts, butyl acetate 50 0 part and 6.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 130 ° C., in the same manner as in Synthesis Example 1, A copolymer as a foam stabilizer of Synthesis Example 31 was obtained. The synthesized copolymer had a weight average molecular weight of 13,900 and an SP value of 9.3.

(Synthesis Example 32)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-32) instead of the dropping solution (b-1) 75.0 parts, phenoxyethyl acrylate (trade name: Viscoat #192: manufactured by Osaka Organic Chemical Industry Co., Ltd.) 25.0 parts, methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation) 150.0 parts , 50.0 parts of butyl acetate and 6.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 130 ° C. Same as in Synthesis Example 1. A copolymer as a foam stabilizer of Synthesis Example 32 was obtained by the method of. The synthesized copolymer had a weight average molecular weight of 10600 and an SP value of 9.3.

(Synthesis Example 33)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-33) instead of the dropping solution (b-1) 87.5 parts, 2,2,2-trifluoroethyl acrylate (trade name: Viscoat 3F: manufactured by Osaka Organic Chemical Industry Co., Ltd.) 12.5 parts, methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: NOF Corporation ), 50.0 parts of butyl acetate and 6.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate, except that the reaction temperature during dropping was set to 130 ° C. A copolymer as a foam stabilizer of Synthesis Example 33 was obtained in the same manner as in Synthesis Example 1. The synthesized copolymer had a weight average molecular weight of 10,100 and an SP value of 9.2.

(Synthesis Example 34)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 75 parts of lauryl acrylate as the dropping solution (b-34) instead of the dropping solution (b-1). 0 parts, 175.0 parts of methoxypolyethylene glycol methacrylate (trade name Miramar M193: manufactured by MIWON), 50.0 parts of butyl acetate and 10.0 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution. A copolymer as a foam stabilizer of Synthesis Example 34 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130°C. The weight average molecular weight of the synthesized copolymer was 9300 and the SP value was 9.2.

(Synthesis Example 35)
Using 120 parts of butyl acetate as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-35) instead of the dropping solution (b-1) 75.0 parts, 175.0 parts of methoxypolyethylene glycol methacrylate (trade name Miramar M193: manufactured by MIWON), 50.0 parts of butyl acetate and tertiary-amylperoxy-2-ethylhexanoate 50% solution 11.0 A copolymer as a foam stabilizer of Synthesis Example 35 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 10,000 and an SP value of 9.3.

(Synthesis Example 36)
120 parts of butyl acetate was used as the solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and 176 parts of lauryl acrylate was used as the dropping solution (b-36) instead of the dropping solution (b-1). 0 parts, 264.0 parts of methoxypolyethylene glycol acrylate (trade name NK Ester AM-130G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 50.0 parts of butyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 36 was obtained in the same manner as in Synthesis Example 1 except that 6.6 parts of the solution was used and the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 15400 and an SP value of 9.4.

(Synthesis Example 37)
Ethyl acrylate 212.5 parts as a dropping solution (b-37) instead of the dropping solution (b-1) of Synthesis Example 1, polyethylene glycol monoacrylate (trade name Blemmer AE-400: manufactured by NOF Corporation) 37.5 Parts, 50.0 parts of propylene glycol monomethyl ether and 12.5 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 120 ° C. Synthesis Example A copolymer as a foam stabilizer of Synthesis Example 37 was obtained in the same manner as in Example 1. The synthesized copolymer had a weight average molecular weight of 7200 and an SP value of 10.2.

(Synthesis Example 38)
Using 120 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, a dropping solution (b-38) instead of the dropping solution (b-1) 2,2- Vinyl dimethyloctanoate (trade name VEOVA 10: manufactured by HEXON) 50.0 parts, methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation) 200.0 parts, butyl acetate 50.0 parts and tertiary -Amylperoxy-2-ethylhexanoate 50% solution 5.5 parts was used, and the foam stabilization of Synthesis Example 38 was performed in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130 ° C. A copolymer was obtained as an agent. The synthesized copolymer had a weight average molecular weight of 9200 and an SP value of 9.2.

(Synthesis Example 39)
Using 120 parts of isobutyl acetate as a solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and 2-ethylhexyl acrylate as a dropping solution (b-39) instead of the dropping solution (b-1) 50.0 parts, 25.0 parts of diethylene glycol monovinyl ether, 175.0 parts of methoxypolyethylene glycol acrylate (trade name Blenmar AME-400: manufactured by NOF Corporation), 50.0 parts of isobutyl acetate and tertiary - amyl peroxy - Copolymerization as a foam stabilizer of Synthesis Example 39 was carried out in the same manner as in Synthesis Example 1, except that 2.0 parts of a 50% solution of 2-ethylhexanoate was used and the reaction temperature during dropping was set to 105 ° C. got a union. The synthesized copolymer had a weight average molecular weight of 11,900 and an SP value of 9.5.

(Synthesis Example 40)
Using 120 parts of isobutyl acetate as the solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-40) instead of the dropping solution (b-1) 50.0 parts, butoxy polyethylene glycol-polypropylene glycol allyl ether (trade name Unisafe PKA-5015: manufactured by NOF Corporation) 25.0 parts, methoxy polyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation) 175.0 parts, 50.0 parts of isobutyl acetate and 6.0 parts of tertiary-amylperoxy-2-ethylhexanoate 50% solution were used, except that the reaction temperature during dropping was set to 130 ° C. Synthesis A copolymer as a foam stabilizer of Synthesis Example 40 was obtained in the same manner as in Example 1. The synthesized copolymer had a weight average molecular weight of 9200 and an SP value of 9.2.

(Synthesis Example 41)
Using 350 parts of isobutyl acetate as a solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and 2-ethylhexyl acrylate as a dropping solution (b-41) instead of the dropping solution (b-1) 60.0 parts, polyethylene glycol diacrylate (trade name Miramar M280: manufactured by MIWON) 140.0 parts, isobutyl acetate 116.7 parts and tertiary-amylperoxy-2-ethylhexanoate 50% solution 20.0 parts was used, and a copolymer as a foam stabilizer of Synthesis Example 41 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 10800 and an SP value of 9.5.

(Synthesis Example 42)
Using 120 parts of isobutyl acetate as the solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and 2-ethylhexyl acrylate as the dropping solution (b-42) instead of the dropping solution (b-1). 75.0 parts, 2,2,2-trifluoroethyl acrylate (trade name: Viscoat 3F: manufactured by Osaka Organic Chemical Industry Co., Ltd.) 25.0 parts, methoxy polyethylene glycol acrylate (trade name: Blemmer AME-400: NOF Corporation ), 50.0 parts of isobutyl acetate and 6.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate, except that the reaction temperature during dropping was set to 130 ° C. A copolymer as a foam stabilizer of Synthesis Example 42 was obtained by the same method as in Synthesis Example 1. The synthesized copolymer had a weight average molecular weight of 10500 and an SP value of 9.7.

(Synthesis Example 43)
Using 120 parts of isobutyl acetate as the solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and using 2-ethylhexyl acrylate as the dropping solution (b-43) instead of the dropping solution (b-1) 50.0 parts, 200.0 parts of methoxypolyethylene glycol acrylate (trade name Brenmer AME-400: manufactured by NOF Corporation), 50.0 parts of isobutyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 43 was obtained in the same manner as in Synthesis Example 1 except that 6.0 parts of the solution was used and the reaction temperature during dropping was set to 130°C. The weight average molecular weight of the synthesized copolymer was 9100 and the SP value was 9.3.

(Synthesis Example 44)
Using 120 parts of isobutyl acetate as a solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and adding 50 parts of stearyl acrylate as a dropping solution (b-44) instead of the dropping solution (b-1). 0 parts, 200.0 parts of methoxypolyethylene glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation), 50.0 parts of isobutyl acetate and tertiary-amylperoxy-2-ethylhexanoate 50% solution 6 A copolymer as a foam stabilizer of Synthesis Example 44 was obtained in the same manner as in Synthesis Example 1, except that 0.0 part was used and the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 7900 and an SP value of 9.2.

(Synthesis Example 45)
Ethyl acrylate 212.5 parts as a dropping solution (b-45) instead of the dropping solution (b-1) of Synthesis Example 1, phenoxyethyl acrylate (trade name Viscoat # 192: manufactured by Osaka Organic Chemical Industry Co., Ltd.) 37.5 Parts, 100.0 parts of propylene glycol monomethyl ether and 25.0 parts of a 50% solution of tertiary-amyl peroxy-2-ethylhexanoate were used, and the reaction temperature during dropping was set to 105 ° C. Synthesis Example A copolymer as a foam stabilizer of Synthesis Example 45 was obtained in the same manner as in Example 1. The synthesized copolymer had a weight average molecular weight of 3400 and an SP value of 10.2.

(Synthesis Example 46)
120 parts of isobutyl acetate was used as the solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and 90 parts of butyl acrylate was used as the dropping solution (b-46) instead of the dropping solution (b-1). 0 parts, 210.0 parts of methoxypolyethylene glycol acrylate (trade name NK Ester AM-230G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of isobutyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 46 was obtained in the same manner as in Synthesis Example 1, except that 4.4 parts of the solution was used and the reaction temperature during dropping was set to 130°C. The synthesized copolymer had a weight average molecular weight of 14400 and an SP value of 9.5.

(Synthesis Example 47)
Using 200 parts of toluene as a solvent (a-4) instead of the solvent (a-1) in Synthesis Example 1, dropping solution (b-1) instead of dropping solution (b-47) Lauryl methacrylate 18.8 Part, 43.8 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 50.0 parts of toluene and tertiary-amylperoxy-2-ethylhexanoate 50% solution 0 A copolymer as a foam stabilizer of Synthesis Example 47 was obtained in the same manner as in Synthesis Example 1, except that 4 parts were used and the reaction temperature during dropping was set to 90°C. The synthesized copolymer had a weight average molecular weight of 67700 and an SP value of 9.4.

(Synthesis Example 48)
Using 400 parts of toluene as a solvent (a-4) instead of the solvent (a-1) in Synthesis Example 1, dropping solution (b-1) instead of dropping solution (b-48) Lauryl methacrylate 37.5 Part, 87.5 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of toluene and tertiary-amylperoxy-2-ethylhexanoate 50% solution 0 A copolymer as a foam stabilizer of Synthesis Example 48 was obtained in the same manner as in Synthesis Example 1, except that 4 parts were used and the reaction temperature during dropping was set to 90°C. The synthesized copolymer had a weight average molecular weight of 88,300 and an SP value of 9.4.

(Synthesis Example 49)
Using 400 parts of isobutyl acetate as a solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and adding 46.5 parts of lauryl methacrylate as a dropping solution (b-49) instead of the dropping solution (b-1). 9 parts, 109.4 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 68.7 parts of isobutyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 49 was obtained in the same manner as in Synthesis Example 1 except that 0.4 parts of the solution was used and the reaction temperature during dropping was set to 90°C. The synthesized copolymer had a weight average molecular weight of 177,100 and an SP value of 9.4.

(Synthesis Example 50)
Using 400 parts of isobutyl acetate as a solvent (a-3) instead of the solvent (a-1) in Synthesis Example 1, and adding 46.5 parts of lauryl methacrylate as a dropping solution (b-50) instead of the dropping solution (b-1). 9 parts, 109.4 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of isobutyl acetate and 50% of tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 50 was obtained in the same manner as in Synthesis Example 1, except that 0.3 part of the solution was used and the reaction temperature during dropping was set to 85°C. The synthesized copolymer had a weight average molecular weight of 296,000 and an SP value of 9.4.

(Synthesis Example 51)
Using 400 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 25.0 parts of isostearyl acrylate as a dropping solution (b-51) instead of the dropping solution (b-1), 2-hydroxyethyl 140.0 parts of acrylate, 60.0 parts of hydroxypropyl acrylate, 25.0 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 150.0 parts of propylene glycol monomethyl ether and tertiary amyl Using 15.0 parts of a 50% solution of peroxy-2-ethylhexanoate, the foam stabilizer of Synthesis Example 51 was prepared in the same manner as in Synthesis Example 1 except that the reaction temperature during dropping was set to 120 ° C. was obtained. The synthesized copolymer had a weight average molecular weight of 2800 and an SP value of 11.5.

(Synthesis Example 52)
68.2 parts of isostearyl acrylate, 95.5 parts of 2-hydroxyethyl acrylate, 40.9 parts of hydroxypropyl acrylate as a dropping solution (b-52) instead of the dropping solution (b-1) of Synthesis Example 1, methoxy polyethylene Glycol acrylate (trade name Blemmer AME-400: manufactured by NOF Corporation) 68.2 parts, propylene glycol monomethyl ether 100.0 parts and tertiary-amylperoxy-2-ethylhexanoate 50% solution 10.0 parts was used, and a copolymer as a foam stabilizer of Synthesis Example 52 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 120°C. The synthesized copolymer had a weight average molecular weight of 4700 and an SP value of 10.4.

(Synthesis Example 53)
125.0 parts of isostearyl acrylate, 12.5 parts of 2-hydroxyethyl acrylate, 5.0 parts of hydroxypropyl acrylate as a dropping solution (b-53) instead of the dropping solution (b-1) of Synthesis Example 1, methoxy polyethylene Glycol acrylate (trade name Blemmer AME-400: manufactured by NOF Corporation) 107.5 parts, propylene glycol monomethyl ether 100.0 parts and tertiary-amylperoxy-2-ethylhexanoate 50% solution 15.0 parts was used, and a copolymer as a foam stabilizer of Synthesis Example 53 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 120°C. The synthesized copolymer had a weight average molecular weight of 2900 and an SP value of 8.8.

(Synthesis Example 54)
100.0 parts of isostearyl acrylate, 12.5 parts of 2-hydroxyethyl acrylate, 5.0 parts of hydroxypropyl acrylate as a dropping solution (b-54) instead of the dropping solution (b-1) of Synthesis Example 1, methoxy polyethylene Glycol acrylate (trade name: Blemmer AME-400: manufactured by NOF Corporation) 132.5 parts, 100.0 parts of propylene glycol monomethyl ether and 2,2-di(tertiary-amylperoxy)butane 55% solution 14.0 A copolymer as a foam stabilizer of Synthesis Example 54 was obtained in the same manner as in Synthesis Example 1, except that the reaction temperature during dropping was set to 120°C. The synthesized copolymer had a weight average molecular weight of 3800 and an SP value of 8.9.

(Synthesis Example 55)
Using 400 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 37.5 parts of isostearyl acrylate as a dropping solution (b-55) instead of the dropping solution (b-1), 2-hydroxyethyl 112.5 parts of acrylate, 50.0 parts of hydroxypropyl acrylate, 50.0 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 150.0 parts of propylene glycol monomethyl ether and 2,2- The foam stabilizer of Synthesis Example 55 was prepared in the same manner as in Synthesis Example 1, except that 15.0 parts of a 55% solution of di(tertiary-amylperoxy)butane was used and the reaction temperature during dropping was set to 120 ° C. A copolymer was obtained as The synthesized copolymer had a weight average molecular weight of 3500 and an SP value of 10.9.

(Synthesis Example 56)
Using 200 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and adding 75 parts of lauryl methacrylate as a dropping solution (b-56) instead of the dropping solution (b-1). 0 parts, 175.0 parts of methoxypolyethylene glycol methacrylate (trade name NK Ester M-40G: manufactured by Shin-Nakamura Chemical Co., Ltd.), 100.0 parts of butyl acetate and 50% tertiary-amylperoxy-2-ethylhexanoate A copolymer as a foam stabilizer of Synthesis Example 56 was obtained in the same manner as in Synthesis Example 1, except that 20.0 parts of the solution was used and the reaction temperature during dropping was set to 120°C. The weight average molecular weight of the synthesized copolymer was 9200 and the SP value was 9.4.

(Synthesis Example 57)
Using 400 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 50.0 parts of isostearyl acrylate as a dropping solution (b-57) instead of the dropping solution (b-1), 2-hydroxyethyl 97.5 parts of acrylate, 40.0 parts of hydroxypropyl acrylate, 62.5 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 150.0 parts of propylene glycol monomethyl ether and tertiary amyl Using 15.0 parts of a 50% solution of peroxy-2-ethylhexanoate, the foam stabilizer of Synthesis Example 57 was prepared in the same manner as in Synthesis Example 1 except that the reaction temperature during dropping was set to 120 ° C. was obtained. The synthesized copolymer had a weight average molecular weight of 2500 and an SP value of 10.6.

(Synthesis Example 58)
Using 400 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 75.0 parts of isostearyl acrylate as a dropping solution (b-58) instead of the dropping solution (b-1), 2-hydroxyethyl 62.5 parts of acrylate, 25.0 parts of hydroxypropyl acrylate, 87.5 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 150.0 parts of propylene glycol monomethyl ether and tertiary amyl Using 15.0 parts of a 50% solution of peroxy-2-ethylhexanoate, the foam stabilizer of Synthesis Example 58 was prepared in the same manner as in Synthesis Example 1 except that the reaction temperature during dropping was set to 120 ° C. was obtained. The synthesized copolymer had a weight average molecular weight of 2600 and an SP value of 9.9.

(Synthesis Example 59)
Using 250 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 87.5 parts of isostearyl acrylate as a dropping solution (b-59) instead of the dropping solution (b-1), 2-hydroxyethyl 35.0 parts of acrylate, 15.0 parts of hydroxypropyl acrylate, 112.5 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 100.0 parts of propylene glycol monomethyl ether and tertiary amyl Using 15.0 parts of a 50% solution of peroxy-2-ethylhexanoate, the foam stabilizer of Synthesis Example 59 was prepared in the same manner as in Synthesis Example 1 except that the reaction temperature during dropping was set to 120 ° C. was obtained. The synthesized copolymer had a weight average molecular weight of 2900 and an SP value of 9.4.

(Synthesis Example 60)
Using 250 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 85.0 parts of isostearyl acrylate as a dropping solution (b-60) instead of the dropping solution (b-1), 2-hydroxyethyl 17.5 parts of acrylate, 7.5 parts of hydroxypropyl acrylate, 140.0 parts of methoxypolyethylene glycol acrylate (trade name Blenmer AME-400: manufactured by NOF Corporation), 50.0 parts of propylene glycol monomethyl ether and tertiary amyl Using 15.0 parts of a 50% solution of peroxy-2-ethylhexanoate, the foam stabilizer of Synthesis Example 60 was prepared in the same manner as in Synthesis Example 1 except that the reaction temperature during dropping was set to 120 ° C. was obtained. The synthesized copolymer had a weight average molecular weight of 2700 and an SP value of 9.1.

(Foam Stabilizer Comparative Example 1)
Using 150 parts of butyl acetate as a solvent (a-2) instead of the solvent (a-1) in Synthesis Example 1, and isostearyl acrylate 293 as a dropping solution (b-h1) instead of the dropping solution (b-1) .0 parts, 30.0 parts of butyl acetate and 2.0 parts of a 50% solution of tertiary-amylperoxy-2-ethylhexanoate, except that the reaction temperature during dropping was set to 130 ° C. Synthesis Example A copolymer as a foam stabilizer in Foam Stabilizer Comparative Example 1 was obtained in the same manner as in Example 1. The synthesized copolymer had a weight average molecular weight of 4600 and an SP value of 8.2.

(Comparative Synthesis Example 2)
Using 400 parts of the solvent (a-1) propylene glycol monomethyl ether of Synthesis Example 1, 175.0 parts of 2-hydroxyethyl acrylate as a dropping solution (b-h2) instead of the dropping solution (b-1), hydroxypropyl 75.0 parts of acrylate, 150.0 parts of propylene glycol monomethyl ether and 15.0 parts of tertiary-amyl peroxy-2-ethylhexanoate 50% solution were used, except that the reaction temperature during dropping was set to 130 ° C. obtained a copolymer as a foam stabilizer in Foam Stabilizer Comparative Example 2 in the same manner as in Synthesis Example 1. The synthesized copolymer had a weight average molecular weight of 2400 and an SP value of 12.3.

(Foam Stabilizer Comparative Example 3)
Foam Stabilizer As a foam stabilizer in Comparative Example 3, a silicone-based foam stabilizer (trade name SH193: manufactured by Dow Toray Industries, Inc.) was prepared.

(Foam Stabilizer Comparative Example 4)
Foam Stabilizer As a foam stabilizer in Comparative Example 4, a silicone foam stabilizer (trade name: L-3184J, manufactured by Momentive) was prepared.

Table 1 shows the compositions and physical properties of Synthesis Examples 1-60 and Foam Stabilizer Comparative Examples 1-2 synthesized as described above.

[Preparation of polyurethane foam]
Next, using the foam stabilizers of Synthesis Examples 1 to 60 and Foam Stabilizer Comparative Examples 1 to 4 obtained as described above, the polyurethane foam raw materials shown in Table 2 below were blended in Examples and Comparative Examples. of polyurethane foam was produced. In addition, in Test Examples 1 to 3 described later, polyurethane foams as "blanks" containing no foam stabilizer were also produced. Specifically, a polyurethane foam was produced as follows.

(material)
As shown in Table 2, as polyols, two types of polyester polyols, specifically RFK-505 manufactured by Kawasaki Kasei Co., Ltd. (hydroxyl value: 250 mg KOH / g, OH equivalent: 224.40) 13.75 and 17.00 parts of FLEXOREZ A308 (hydroxyl value: 260 mgKOH/g, OH equivalent: 215.77) manufactured by King Industries. The SP value of these polyols (mixture) was 11.9 (measured by turbidity point titration method).

Also, 0.60 parts of water and 4.00 parts of cyclopentane (manufactured by Tokyo Chemical Industry Co., Ltd.) were used as foaming agents.

Also, as a trimerization catalyst, 0.70 parts of TOYOCAT TR-20 manufactured by Tosoh Corporation and 0.50 parts of potassium 2-ethylhexanoate manufactured by Tokyo Chemical Industry Co., Ltd. were used, and as a resinification catalyst (metal catalyst) , 0.10 parts of K-KAT 348 manufactured by King Industries, and 0.60 parts of tetramethylethylenediamine manufactured by Tokyo Chemical Industry Co., Ltd. was used as a foaming catalyst.

Furthermore, as the polyisocyanate, Millionate MR-200 (NCO content: 31%, NCO equivalent: 135.48) manufactured by Tosoh Corporation, which is poly-MDI (diphenylmethane diisocyanate), was used.

The isocyanate index of the polyurethane foam obtained with the formulation shown in Table 2 is 450.

(Manufacturing method)
Each raw material described in Part A of Table 2 and any of the foam stabilizers of Synthesis Examples 1 to 60 and Foam Stabilizer Comparative Examples 1 to 4 were sequentially added and mixed with stirring using a Lab Disper. Next, a total of 18.6 g of each raw material listed in Part A of Table 2, the above foam stabilizer (polyol mixture Mo), and 52.9 g of the polyisocyanate listed in Part B of Table 2 are sequentially added to the polycup. were mixed while stirring by hand stirring. The foam stabilizer is described in Tables 3 to 5 below, based on the total amount of polyurethane foam raw materials (the total amount of each raw material described in Part A and the polyisocyanate and foam stabilizer described in Part B). It was blended in the specified amount (% by mass).

[Method for evaluating effect of imparting foam stabilizing ability and adhesive strength]
The foam stabilizing ability of the blowing agent and the effect of imparting adhesive strength to the polyurethane foam were evaluated for the polyurethane foam produced as described above.

(Evaluation of foam stabilizing ability)
The foam stabilizing ability of the foam stabilizers of Synthesis Examples and Foam Stabilizer Comparative Examples was evaluated by measuring the bulkiness (foam volume) and cell diameter of the polyurethane foams obtained as described above. The larger the bulkiness of the polyurethane foam and the smaller the cell diameter of the polyurethane foam, the more excellent the foam stabilizer becomes. Specifically, the bulkiness and cell diameter of the polyurethane foam were evaluated according to the following criteria. The cell diameter of the polyurethane foam was measured by microscopic observation of the cross section of the obtained polyurethane foam sample.
<Bulk height of polyurethane foam (foam volume)>
5 Foaming volume of 1200 mL or more 4 Foaming volume of 1000 mL or more and less than 1200 mL 3 Foaming volume of 800 mL or more and less than 1000 mL 2 Foaming volume of 600 mL or more and less than 800 mL 1 Foaming volume of less than 600 mL <Polyurethane foam cell diameter>
5 Bubble diameter is less than 0.5 mm 4 Bubble diameter is 0.5 mm or more and less than 1.0 mm 3 Bubble diameter is 1.0 mm or more and less than 2.0 mm 2 Bubble diameter is 2.0 mm or more and less than 3.0 mm 1 Bubble diameter is 3.0 mm or more. 0 mm or more

(Evaluation of adhesive strength)
As shown in FIG. 1, base materials 1a and 1b (two sheets) having a thickness of 2 mm to which polyurethane foam is to be adhered were placed on a jig (not shown) with a spacer 2 interposed therebetween so as to have a predetermined gap. . Next, the urethane raw material mixture Mu (mixed solution) of the polyurethane foam raw materials obtained as described above is injected into the gap between the two substrates placed on the jig to form the substrate 1a and the substrate 1b. A tensile shear test piece P was prepared by laminating with a polyurethane foam 3. After allowing the test piece to stand at 20° C. for 2 days, the tensile shear bond strength was measured. 1(a) is a side view of the tensile shear test piece P, and FIG. 1(b) is a top view of the tensile shear test piece P. As shown in FIG. Although the polyurethane foam 3 cannot actually be seen from the upper surface of the tensile shear test piece P, in FIG. clearly shown.

The tensile shear bond strength was measured using a Tensilon RTE-1210 tensile tester (manufactured by A&D Co., Ltd.). Specifically, both ends of the test piece P are fixed to the above tensile tester, pulled at a tensile speed of 10 mm / min (constant moving speed), and the maximum load F (N) until the test piece P is destroyed It was measured. This maximum load F (N) was divided by the cross-sectional area A (mm ² ) of the test piece P, and the bonding strength S (kPa) was determined by the following formula (3).
S=F/A·10 ³ (3)

Based on the adhesive strength S (kPa) obtained as described above, the adhesive strength of the polyurethane foam to the substrate was evaluated according to the following criteria.
5 Adhesion strength S is 140 kPa or more 4 Adhesion strength S is 120 kPa or more and less than 140 kPa 3 Adhesion strength S is 100 kPa or more and less than 120 kPa 2 Adhesion strength S is 80 kPa or more and less than 100 kPa 1 Adhesion strength S is less than 80 kPa

[Test Example 1: Example of adhering polyurethane foam to a polypropylene resin substrate]
In Test Example 1, the foam stabilizers of Synthesis Examples 1 to 60 and Foam Stabilizer Comparative Examples 1 to 4 were blended in the amounts (% by mass) shown in Table 3 below, using a urethane raw material mixture Mu of polyurethane foam raw materials. This is an example of evaluating the performance of the polyurethane foams produced in Examples 1-1 to 1-64 and Comparative Examples 1-1 to 1-4. In this test example, the foam stabilizing ability of the foam stabilizers used in Examples 1-1 to 1-64 and Comparative Examples 1-1 to 1-4 was evaluated by the method described above. Polypropylene (PP) resin was used as the substrates 1a and 1b, and the adhesion of the polyurethane foam 3 to the substrates 1a and 1b was evaluated. These evaluation results are shown in Table 3.

As shown in Table 3, all of the polyurethane foams of Examples 1-1 to 1-64 had foam stabilizing ability and adhesion at a practical level (evaluation of 2 or higher).

Here, from a comparison of Examples 1-39, 1-40 and 1-43, as the polymerizable unsaturated monomer (A), a polymerizable unsaturated monomer in which R1 in general formula (1) is an acrylic group was used alone. When the polymerizable unsaturated monomer in which R1 is an acrylic group and the polymerizable unsaturated monomer in which R1 is a vinyl ether group are used in combination, and when the polymerizable unsaturated monomer in which R1 is an acrylic group and the polymerizable unsaturated monomer in which R1 is an allyl group are used in combination, It can be seen that all of the cases in which a certain polymerizable unsaturated monomer is used in combination have excellent foam stabilizing ability and high adhesion even to difficult-to-adhere substrates such as PP resin. Among them, as the polymerizable unsaturated monomer (A), when a polymerizable unsaturated monomer in which R1 in the general formula (1) is an acrylic group is used alone, when used in combination with other polymerizable unsaturated monomers It had a higher adhesive strength to difficult-to-adhere substrates.

Next, from a comparison of Examples 1-43 and 1-44, the larger the number of carbon atoms in the hydrophobic group of the polymerizable unsaturated monomer (B), the higher the foam stabilizing ability, but the lower the adhesive strength. Also found to be. From a comparison between Examples 1-21 and 1-44, it can be seen that the presence of a branched chain in the hydrophobic group of the polymerizable unsaturated monomer (B) slightly reduces the foam stabilizing ability, while increasing the adhesive force. I understand. This is presumed to be due to the fact that the straight-chain hydrophobic group has lower affinity with the surface of the difficult-to-adhere base material such as PP resin.

Next, from a comparison of Examples 1-22 and 1-61 to 1-64, it can be seen that the more the amount of the foam stabilizer added, the higher the foam-stabilizing ability, but the lower the adhesive strength. From the viewpoint of enhancing the foam stabilizing ability, the amount of the foam stabilizer is preferably 0.7% by mass or more, more preferably 1.5% by mass or more. In addition, from the viewpoint of increasing the adhesive strength, the amount of the foam stabilizer is preferably 2.5% by mass or less, more preferably 1.5% by mass or less, and 0.7% by mass or less. It is even more preferable to have

Next, from a comparison of Examples 1-51 to 1-55 and 1-57 to 60, the SP value of the foam stabilizer is lower than the SP value of the polyol, and the difference between the SP values is 1.0 or more. When it is 8 or less, the foam stabilizing ability can be enhanced while maintaining good adhesive strength (evaluation of 3 or more). From the viewpoint of further increasing the foam stabilizing ability, the SP value difference is more preferably 1.3 or more, and further preferably 1.5 or more and 2.0 or less.

Next, from a comparison of Examples 1-26, 1-27, 1-47 to 50 and 1-56, the weight average molecular weight of the copolymer used as a foam stabilizer is above the practical level when it is 5000 to 500000. It can be seen that it has a high foam stabilizing ability while maintaining adhesive strength to difficult-to-adhere substrates. When the weight-average molecular weight exceeds 500,000, although it has a high foam stabilizing ability, poorly dispersed substances (undispersed aggregates) are generated (see Example 1-27), and the effect of the foam stabilizing agent is sufficiently exhibited. Therefore, the weight average molecular weight is preferably 500,000 or less.

Example 6 is an example in which a polymerizable unsaturated monomer (B) having many branched hydrophobic groups is used. Thus, when the hydrophobic group has a large number of branched portions, the hydrophobic group tends to be oriented on the surface, resulting in relatively low adhesion to the difficult-to-adhere base material. On the other hand, Example 38 is an example in which the same polymerizable unsaturated monomer (B) as in Example 6 is used, and the blending amount of the polymerizable unsaturated monomer (B) is less than in Example 6. . As a result, it can be seen that although the foam stabilizing ability was slightly lowered, the adhesive strength to difficult-to-adhere substrates was greatly improved.

Example 14 is an example in which the blending amount of the polymerizable unsaturated monomer (B) is as large as 60%. Therefore, in Example 14, although the foam stabilizing ability was high, the adhesion to the difficult-to-bond substrate was relatively low. On the other hand, Example 46 is an example in which the same polymerizable unsaturated monomer (B) as in Example 14 is used, and the blending amount of the polymerizable unsaturated monomer (B) is less than in Example 14. . As a result, it can be seen that although the foam stabilizing ability was slightly lowered, the adhesive strength to difficult-to-adhere substrates was greatly improved.

On the other hand, Comparative Example 1-1, which used a foam stabilizer synthesized without blending the polymerizable unsaturated monomer (A), resulted in inferior foam stabilizing ability and adhesive strength to difficult-to-adhere substrates. . Further, Comparative Example 1-2, which used a foam stabilizer synthesized without blending the polymerizable unsaturated monomer (B), resulted in inferior foam-stabilizing performance. Furthermore, Comparative Examples 1-3 and 1-4 using a silicone-based foam stabilizer resulted in poor adhesion to difficult-to-adhere substrates.

[Test Example 2: Example of adhering polyurethane foam to a polyethylene resin substrate]
In Test Example 2, the foam stabilizers of Synthesis Examples 2, 5, 7, 9, 10, 13, 15, 21, 22, 25, 28, and 34 and Foam Stabilizer Comparative Examples 1 and 3 were used as shown in Table 4 below. The performance of the polyurethane foams of Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-2 prepared using the urethane raw material mixture Mu of the polyurethane foam raw material blended in the compounding amount (% by mass) was evaluated. For example. In this test example, polyethylene (PE) resin was used as the substrates 1a and 1b of the tensile shear test piece P for Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-2 by the method described above. , the adhesive strength of the polyurethane foam 3 to the substrates 1a and 1b was evaluated. These evaluation results are shown in Table 4.

As shown in Table 4, when the PE resin was used as the base material, the adhesive strength to the hard-to-bond base material was generally inferior to that when the PP resin was used as the base material (Test Example 1). However, almost the same tendency as in Test Example 1 was shown.

[Test Example 3: Reference Example in which Polyurethane Foam is Adhered to a Polyacetal Resin Substrate]
Test Example 3 is a urethane raw material mixture of polyurethane foam raw materials in which the foam stabilizers of Synthesis Examples 16, 21, 25, and 34 and Foam Stabilizer Comparative Examples 3 and 4 are blended in the amounts (% by mass) shown in Table 5 below. This is an example of evaluating the performance of the polyurethane foams of Reference Examples 3-1 to 3-6 produced using Mu. In this test example, polyacetal (POM) resin was used as the substrates 1a and 1b of the tensile shear test piece P for Reference Examples 3-1 to 3-6 by the method described above, and the substrates 1a and 1b of the polyurethane foam 3 were used. was evaluated. These evaluation results are shown in Table 5. The adhesive strength shown in Table 5 is not an index based on the evaluation criteria described above, but an actual measurement value of adhesive strength S (kPa) in a tensile shear test.

As shown in Table 5, when the POM resin was used as the base material, the adhesion to the base material was also high in Reference Examples 3-5 and 3-6 using the silicone foam stabilizer. On the other hand, in Reference Examples 3-1 to 3-4 using the foam stabilizers of Synthesis Examples 16, 21, 25 and 34, Reference Examples 3-5 and 3-6 using silicone foam stabilizers The result was much higher than the adhesive strength of Thus, even with a substrate that does not have a problem with adhesion to polyurethane foam when a silicone foam stabilizer is used, the foam stabilizer of the present invention can be used to prevent the use of a silicone foam stabilizer. It was suggested that the adhesive force to the substrate is enhanced more than when

Claims

A foam stabilizer for polyurethane foam mixed with a polyisocyanate and a polyol and used in the production of polyurethane foam,
Containing a copolymer containing 5 to 95% by mass of structural units derived from the polymerizable unsaturated monomer (A) and 5 to 95% by mass of structural units derived from the polymerizable unsaturated monomer (B) cage,
The polymerizable unsaturated monomer (A) is at least one ether group-containing monomer represented by the following general formula (1),
R1-( CmH2mO ) n -R2 ( 1)
(In the general formula (1), R1 is a (meth)acryl group, R2 is a hydrogen atom, a (meth)acryl group, an alkyl group having 1 to 22 carbon atoms or an aryl group, and m is 2 is a natural number from ~4, and n is a natural number from 1 to 100.)
The polymerizable unsaturated monomer (B) is at least one monomer selected from the group of polymerizable unsaturated monomers that do not satisfy the general formula (1) and have a hydrophobic group, Foam stabilizer for polyurethane foam.
The foam stabilizer for polyurethane foam according to claim 1, characterized in that the SP value of said foam stabilizer is 1.0 to 3.1 lower than the SP value of said polyol.
The foam stabilizer for polyurethane foam according to claim 1 or 2, wherein the copolymer has a weight average molecular weight of 1,000 to 500,000.
Claim 1, wherein the copolymer contains, as the polymerizable unsaturated monomer (A), only a polymerizable unsaturated monomer in which R1 in the general formula (1) is a (meth)acrylic group. 4. The foam stabilizer for polyurethane foam according to any one of -3.
The polyurethane foam according to any one of claims 1 to 4, wherein the hydrophobic group of the polymerizable unsaturated monomer (B) is a linear, branched or cyclic hydrocarbon group. foam stabilizer.
The polyurethane foam according to any one of claims 1 to 5, wherein the hydrophobic group of the polymerizable unsaturated monomer (B) does not contain an oxygen atom, a nitrogen atom, a fluorine atom and a silicon atom. Foam stabilizer.
Obtained by foaming and curing a urethane raw material mixture containing at least a polyisocyanate, a polyol, and the foam stabilizer for polyurethane foam according to any one of claims 1 to 6,
A polyurethane foam, wherein the urethane raw material mixture contains 0.1% by mass to 5.0% by mass of the foam stabilizer.
The polyurethane foam according to claim 7, wherein the SP value of the foam stabilizer is 1.0 to 3.1 lower than the SP value of the polyol.
A polyurethane foam lamination obtained by laminating a substrate selected from the group consisting of polypropylene resin, polyethylene resin, fluororesin and silicone resin, or a substrate coated with wax, and the polyurethane foam according to claim 7 or 8. body.
A method for producing a foam stabilizer for polyurethane foam mixed with polyisocyanate and polyol and used for producing polyurethane foam, comprising:
A polymerization step of obtaining a copolymer by copolymerizing a monomer mixture containing 5 to 95% by mass of a polymerizable unsaturated monomer (A) and 5 to 95% by mass of a polymerizable unsaturated monomer (B). ,
The polymerizable unsaturated monomer (A) is at least one ether group-containing monomer represented by the following general formula (1),
R1-( CmH2mO ) n -R2 ( 1)
(In the general formula (1), R1 is a (meth)acryl group, R2 is a hydrogen atom, a (meth)acryl group, an alkyl group having 1 to 22 carbon atoms or an aryl group, and m is 2 is a natural number from ~4, and n is a natural number from 1 to 100.)
The polymerizable unsaturated monomer (B) is at least one monomer selected from the group of polymerizable unsaturated monomers that do not satisfy the general formula (1) and have a hydrophobic group, A method for producing a foam stabilizer for polyurethane foam.
The method for producing a foam stabilizer for polyurethane foam according to claim 10, wherein the SP value of the foam stabilizer is 1.0 to 3.1 lower than the SP value of the polyol.
The method for producing a foam stabilizer for polyurethane foam according to claim 10 or 11, wherein the copolymer has a weight average molecular weight of 1,000 to 500,000.
Claim 10, wherein the copolymer contains, as the polymerizable unsaturated monomer (A), only a polymerizable unsaturated monomer in which R1 in the general formula (1) is a (meth)acrylic group. 13. The method for producing a foam stabilizer for polyurethane foam according to any one of 12.
The polyurethane foam according to any one of claims 10 to 13, wherein the hydrophobic group of the polymerizable unsaturated monomer (B) is a linear, branched or cyclic hydrocarbon group. A method for producing a foam stabilizer for
The polyurethane foam according to any one of claims 10 to 14, wherein the hydrophobic group of the polymerizable unsaturated monomer (B) does not contain an oxygen atom, a nitrogen atom, a fluorine atom and a silicon atom. A method for producing a foam stabilizer.
A foam stabilizer mixing step of mixing a polyol and the polyurethane foam foam stabilizer according to any one of claims 1 to 6 to obtain a polyol mixture;
a foam production step of foaming and curing the polyol mixture and polyisocyanate while mixing to obtain a polyurethane foam;
A method for producing a polyurethane foam, comprising:
A lamination step of laminating a substrate selected from the group consisting of polypropylene resin, polyethylene resin, fluororesin and silicone resin, or a substrate coated with wax, and polyurethane foam,
A method for producing a polyurethane foam laminate, wherein in the laminating step, the polyurethane foam is a foam obtained by the method for producing a polyurethane foam according to claim 16.