JPH1087995A - Foamable resin composition, foam using the same, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To heat a hard, semi-rigid or soft foam having good paintability, adhesiveness, etc., good foam regulating properties and high expansion ratio, at room temperature or at a relatively low temperature. The present invention provides a foamable resin composition obtained below, a foam using the foamable resin composition, and a method for producing the same. The foamable resin composition comprises (A) an organic compound having a carbon-carbon double bond, (B) a compound having a SiH group having a specific structure, and (C) a compound having an OH group. In addition, at least a part of the component (B) contains a polyorganohydrogensiloxane modified with a polyoxyalkylene chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel foamable resin composition characterized in that a foam is formed by foaming and curing under heating at room temperature or at a relatively low temperature, and uses the composition. And a method for producing the same.

More specifically, the present invention provides sound insulation, heat insulation,
The present invention relates to a foam that can be suitably used for applications such as water stoppage, airtightness, vibration suppression, protection, cushioning, and decoration, a method for producing the foam, and a foamable resin composition used therefor. Specific examples of the applications include cushioning materials for vehicles, ceiling materials, door trim material, floor cushion vibration damping and sound absorbing materials, car cooler insulation materials, damper air seal materials, waterproof materials, gaskets, air filters, center pillar garnishes ,
Headliner, quarter trim, dust cover, fuel tank safety foam, oil filter,
Ships such as flexible containers, crash pads, sun visors, headrests, insulators, dashboards, door panels, pillars, console boxes, energy absorption bumpers, insulation materials for refrigerated vehicles, cold storage vehicles, tank trucks, refrigerated container vehicles, etc. Insulation material, buoyancy material, FRP board core material, buoy, etc., cushioning material for bedding, cushioning material for furniture, packing material, etc., filters for electric and electronic equipment, sound absorbing heat insulating material, printer sound absorbing material, head Horn ear pat etc.
Cushioning material for packaging, insulation for roofs, ceilings, walls, floors for buildings, covers for water pipes, core materials such as door panels, sizing panels, metal and sizing panels, core materials for partition panels, tatami mats and bran cores Materials, insulation core materials such as bathtubs,
Jointing materials, sealing materials, adhesives, system ceiling insulation panels, roof insulation and waterproofing materials, airtight insulation materials for freezing warehouses and airtight warehouses, heat insulation and cooling materials for plant tanks and piping, refrigerators, freezers, and electronics for home appliances Insulation materials such as jars, anti-condensation materials for room coolers, sports equipment, medical products and cosmetic puffs, shoulder pads, slippers, sandals, sword mountains,
Living goods such as toys are used. In addition, the foamable resin composition of the present invention, a foam using the foamable resin composition, and a method for producing the same can also be used for molding an article shape in a casting method, producing a model sample from a mold, producing a decorative article, and the like. It is.

[0003]

2. Description of the Related Art Conventionally, as a foam of a polymer compound,
Polystyrene, polyethylene, polypropylene, polyvinyl chloride, etc. are used as bead foams or foam sheets and boards, taking advantage of their properties such as heat insulation, light weight, and cushioning, and are used in civil engineering and construction, packaging, household appliances, automobiles, etc. It is used for However, all of these require a large amount of energy for foam molding, and have the problem that so-called in-situ foaming cannot be performed.

On the other hand, a method of obtaining a foam by injection, spraying, or the like, is more advantageous in that there is no gap and high heat insulation when used as a heat insulating material, as compared with the use of a so-called regular foam. When used, there are advantages such as shortening of the construction period and low transportation cost.
A typical example of these foams is urethane foam. As a method for producing this urethane foam, a method using a blowing agent such as chlorofluorocarbon, a method using carbon dioxide generated by the addition of water, which has recently been used, and the like are known. However,
The obtained foam has a problem in weather resistance, cannot be used for exposed parts outdoors, and there is a concern about toxicity of the isocyanate used as a raw material, and there is a problem in workability. There is a concern about the generation of gas and other problems. In addition, the specific fluorocarbon gas used as a foaming agent may destroy the ozone layer, conversion to a safer gas is underway, and technology using water as an alternative foaming agent is still insufficient. The use of such organic foaming agents has problems such as the possibility of fire during construction, and measures are being considered.

Accordingly, silicone foams made of polysiloxane compounds have been developed as foams which have solved the above-mentioned problems such as the weather resistance of urethane foams. This is achieved by using a hydrogen gas or the like generated during a condensation reaction between the hydrosilyl group of the hydrosilyl group-containing polysiloxane and the silanol group of the silanol group-containing polysiloxane compound or the hydroxyl group of the alcohol compound to foam the same hydrosilyl group. It cures by a condensation reaction with a silanol group or a hydrosilylation reaction between a hydrosilyl group and an unsaturated group of an unsaturated group-containing polysiloxane to obtain a foam, and is used as a heat insulating material, an electric insulating material, and a potting agent. ing.

However, when the present inventors tried to use this silicone foam for producing sealing materials, interior / exterior materials, model samples, and decorative articles in civil engineering construction, and for producing decorative articles, the obtained silicone foam was used as a paint, especially recently used. It has been found that there is a problem that it is difficult to apply general coatings by repelling an increasing amount of water-based coatings. In addition, it has been found that even if an attempt is made to bond another substrate or component such as a siding board or wallpaper to the surface of the obtained silicone foam using an adhesive, there is a problem that the adhesive is not bonded with a general adhesive. .

[0007] Furthermore, since silicone foam has a low Tg and is based on a highly flexible polysiloxane as a main component, only a soft foam can be obtained as a foam which can be practically used. It cannot be used to replace rigid and semi-rigid urethane foam in applications.

In addition, even when used in applications where compressive strength is not required, the raw material polysiloxane compound is usually more expensive than the corresponding organic material, and the expansion ratio reaches only about 10 times. Therefore, the obtained foam is expensive, and has a problem that its application field is limited to special applications requiring extremely high flame retardancy such as a nuclear power plant. Methods for reducing the price per unit volume of the body continue to be developed.
However, it is difficult to obtain a sufficient foaming ratio of a silicone foam even if it is intended to obtain a high foam of 15 times or more by hydrogen foaming. Even if a high foam is produced by an extreme composition, only a very brittle foam is used. It was not obtained and could not be put to practical use.

Further, Japanese Patent Publication No. 6-45713 discloses a silicone foam composition from which a foam having improved tensile strength can be obtained by adding a silicone polyimide block copolymer having an organovinylsiloxane unit. However, also in this composition, a component having a siloxane skeleton in the molecule is used as a component having a carbon-carbon double bond, so that similar to a general silicone foam, there is a problem of repelling paint and adhesion by an adhesive. It has problems such as difficulty.

Further, JP-A-3-188166 discloses that (A) an organic polymer containing at least one alkenyl group in a molecule, and (B) an organic polymer containing at least two hydrosilyl groups in a molecule. A compound containing an aliphatic unsaturated bond is disclosed as an example of a storage stability improver in a curable composition comprising a polymer, (C) a hydrosilylation catalyst, and (D) a storage stability improver. As one of them, propargyl alcohol is disclosed. Foam sealants are also shown as one of the many uses for curable compositions. However, there is no description at all about the production of a foam from a composition using propargyl alcohol as the component (D), and no specific disclosure of the method.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and has good weather resistance, good paintability and good adhesion, no generation of harmful gas during combustion, and is hard, semi-hard or soft. It is an object of the present invention to provide a foam which can be substituted for urethane foam, especially a foam having an expansion ratio of 2 times or more, in which useful characteristics as a foam are remarkable, and a method for producing the same. In addition, the above foam can be obtained by foaming and curing under heating at room temperature or at a relatively low temperature, so that foaming can be performed in-situ, and since it does not contain isocyanate, it has low toxicity, and the price per unit volume is relatively low. It is an object of the present invention to provide a foamable resin composition used for producing the foam, which can be used for various uses as a substitute for urethane foam.

[0012]

According to a first aspect of the present invention, there is provided a foamable resin composition comprising (A) a carbon-carbon double bond and a siloxane unit in the molecular skeleton. (B) a compound having SiH, (C) a compound having an OH group, and (B)
At least a part of the component contains a polyorganohydrogensiloxane modified with a polyoxyalkylene chain.

According to a second aspect, the polyorganohydrogensiloxane contained as at least a part of the component (B) in the first aspect has the following formula (1)
Or it has the structure shown by Formula (2).

[0014]

Embedded image (However, m ≧ 2, n, l, p ≧ 0, 10 ≦ (m + n +
l) × p ≦ 80, and R ¹ has a molecular weight of 100 to 10
000 polyoxyalkylene chain; R ² , R ³ ,
R ⁴ and R ⁵ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain one or more phenyl groups. )

Embedded image (However, m ≧ 2, n, l, p ≧ 0, 3 ≦ (m + n +
l) × p ≦ 20, and R ¹ has a molecular weight of 100 to 10
2,000 polyoxyalkylene chains, and R ² , R
³ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more phenyl groups. According to a third aspect, in the second aspect, R ¹ in the formula (1) or the formula (2) representing the polyorganohydrogensiloxane mainly comprises oxyethylene units.

A fourth aspect of the present invention is the composition according to any one of the first to third aspects, wherein the molecular skeleton of the organic compound as the component (A) is carbon, oxygen, hydrogen, nitrogen, sulfur, or halogen. It consists of only one or more of these elements.

According to a fifth aspect, in the first aspect, the molecular skeleton of the organic compound (A) is a polyether-based organic polymer skeleton.

According to a sixth aspect, in the first aspect, the molecular skeleton of the organic compound (A) is a polyester-based organic polymer skeleton.

In a seventh aspect, the organic compound of the component (A) is any one of the following formulas (3) to (5): It has at least one kind of structure as a molecular skeleton.

[0019]

Embedded image

Embedded image

Embedded image (However, in the formulas (3) to (5), R ⁶ represents H or CH ³ , and R ⁷ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R
¹⁷ shows C, H, N, O, S, a divalent substituent of 0-6 carbon atoms containing a halogen only as an element, R ^9, R
¹⁰ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ^{19 each} represent a monovalent substituent having 0 to 6 carbon atoms, and X and Y represent C,
Containing only H, N, O, S, halogen, carbon number 0-10
Represents a divalent substituent. In the formulas (3) and (4), n, m, l, and s represent integers of 1 to 300,
p and q each represent an integer of 0 to 3, and in the formula (5),
n and m show the integer of 0-4. An eighth aspect of the present invention is the organic compound according to any one of the first to seventh aspects, wherein the number of carbon-carbon double bonds in the organic compound as the component (A) is 2 or more per molecule on average. is there.

A ninth aspect is the composition according to any one of the first to eighth aspects, wherein the compound having an OH group as the component (C) is an organic compound in which the OH group is directly bonded to a carbon atom. Compound and / or water.

According to a tenth aspect, in the composition according to any one of the first to eighth aspects, the compound having an OH group as the component (C) is selected from alcohol, carboxylic acid, and water. Or more.

An eleventh aspect is the one according to any one of the first to tenth aspects, wherein (A) to (C)
In addition to the components, a foaming agent is added as the component (D).

In the method for producing a foam according to the twelfth aspect, the foamable resin composition according to any one of the first to eleventh aspects is foamed and cured at a temperature of 100 ° C. or less.

The foam of the present invention is obtained by foaming and curing the foamable resin composition of any one of the first to eleventh aspects at a temperature of 100 ° C. or less.

According to a fourteenth aspect of the present invention, there is provided the foamable resin composition according to any one of the first to eleventh aspects, wherein the components (A) to (C) or the components (A) to (D) are included. Is mixed immediately before use and the mixture is applied directly to the substrate surface and foamed in situ.

According to a fifteenth aspect of the present invention, the foamable resin composition according to any one of the first to eleventh aspects has the components (A) to (C) or the components (A) to (D). Is mixed and foamed immediately before use.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The foamable resin composition of the present invention comprises:
(A) an organic compound having a carbon-carbon double bond and no siloxane unit in the molecular skeleton, (B) a compound having SiH, and (C) a compound having an OH group as essential components, and It is characterized in that at least a part of the component (B) contains a polyorganohydrogensiloxane modified with a polyoxyalkylene chain.

In the foamable resin composition of the present invention,
A hydrosilylation reaction in which the component (B) and the component (C) react to generate hydrogen gas to generate foam, and the component (A) and the component (B) form a Si—C bond having excellent weather resistance. By performing the addition-type crosslinking reaction, the resin is cured to form a foam having excellent weather resistance.

That is, in the foamable resin composition of the present invention, an organic compound containing no siloxane unit in the molecular skeleton is used as the component (A). Polysiloxane is also used as a component having a carbon double bond, and the compressive strength, paintability, adhesiveness, and contamination are lower than those of the silicone foams disclosed in the prior art, in which the composition components are mostly composed of polysiloxane components. It is possible to obtain one having improved properties, dust adhesion and the like. In addition, by changing the component (A) in various ways, one having a wide range of physical properties such as hard to semi-hard and soft can be obtained. Furthermore, since the organic compound of the component (A) does not contain a siloxane bond in the molecular skeleton, many of them are relatively inexpensive, and as a result, an inexpensive foam is easily obtained. In addition, by increasing the expansion ratio, a foam having a low price per unit volume can be obtained. On the other hand, by using a compound having a specific structure as the component (B), the foam-regulating property of the system is greatly improved, and as a result, a foam having fine cells and a high expansion ratio can be obtained. it can.

The components (A) to (C) will be described below in order.

First, the component (A), an organic compound having a carbon-carbon double bond and having no siloxane skeleton in its molecular skeleton (hereinafter, simply referred to as skeleton) will be described.

In the component (A), when its molecular structure is considered as being divided into a skeleton portion and an alkenyl group having a carbon-carbon double bond bonded to the skeleton by a covalent bond, the carbon-carbon The alkenyl group having a heavy bond may be present anywhere in the molecule, but is preferably present on the side chain or terminal from the viewpoint of reactivity.

The skeleton of the component (A), which is an organic compound, is made of polysiloxane to solve the problems of gas permeability and repellency.
Siloxane units (Si-OS) such as organic block copolymers and polysiloxane-organic graft copolymers
not containing i), but as constituent elements carbon, oxygen,
The structure is not particularly limited as long as it is a skeleton containing at least one of hydrogen, nitrogen, sulfur, and halogen, and may be a general organic polymer skeleton or organic monomer skeleton. For example, it is a skeleton of a polyether type, a polyester type, a polycarbonate type, a saturated hydrocarbon type, a polyacrylate type, a polyamide type, a phenol-formaldehyde type (phenol resin type) or the like. Examples of the monomer skeleton include phenol-based, bisphenol-based, and mixtures thereof.

Of these, the polyether-based polymer skeleton is suitably used for obtaining a soft foam. Examples thereof include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-
And polyoxypropylene copolymers. As a more specific example,

Embedded image (However, R ²⁰ and R ²¹ are C, H, N,
It represents a divalent organic group having 1 to 6 carbon atoms containing only O, S, and halogen, and n, m, and l represent integers of 1 to 300. )
Is mentioned.

On the other hand, other polymer skeletons having a higher Tg than the polysiloxane skeleton are also suitably used for obtaining a foam. For example, condensation of dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid with glycols such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol, or ring opening of lactones. Polyester polymer obtained by polymerization, ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, copolymer of styrene and the like, Obtained by hydrogenating polybutadiene, a copolymer of butadiene with styrene, acrylonitrile, etc., or a copolymer of polyisoprene, polybutadiene, isoprene or a copolymer of butadiene with acrylonitrile, styrene, etc. Li olefinic (saturated hydrocarbon) polymers, ethyl acrylate, polyacrylic acid ester monomer is a obtained by radical polymerization such as butyl acrylate, ethyl acrylate, acrylic acid esters and vinyl acetate and butyl acrylate,
Acrylonitrile, methyl methacrylate, acrylate copolymers with styrene, etc., a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer,
Nylon 6 by ring-opening polymerization of polysulfide polymer, ε-aminocaprolactam, Nylon 66 by polycondensation of hexamethylenediamine and adipic acid, Nylon 61 by polycondensation of hexamethylenediamine and sebacic acid
Nylon 1 by polycondensation of 0, ε-aminoundecanoic acid
1. Nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide polymer such as copolymerized nylon having two or more of the above-mentioned nylons, for example, produced by polycondensation from bisphenol A and carbonyl chloride. Polycarbonate polymer, diallyl phthalate polymer, phenol-formaldehyde (phenol resin) skeleton include, for example, novolak phenol resin, resole phenol resin, ammonia resole phenol resin, benzylic ether phenol Resins.

An alkenyl group having a carbon-carbon double bond is introduced into these polymer skeletons to form the organic compound (A).

The alkenyl group is not particularly limited as long as the addition reaction by the hydrosilylation reaction with the component (B) is possible, but the alkenyl group represented by the following formula (6) is preferable from the viewpoint of reactivity. is there.

[0038]

Embedded image (However, R ⁶ represents hydrogen or a methyl group.) Among them, from the viewpoint of availability of raw materials,

Embedded image Is particularly preferred.

The alkenyl group only needs to be bonded to the skeleton portion of the component (A) via a divalent or higher valent substituent, and the divalent or higher valent substituent has C, H, N, O, Carbon number 0 containing only one or more of S and halogen
The substituent is not particularly limited as long as it is 10, and as a specific example,

Embedded image Is mentioned. Also, two or more of these divalent or more substituents may be connected by a covalent bond to form one divalent or more substituent.

As a method of introducing an alkenyl group into the polymer skeleton, various methods can be used. The method includes introducing an alkenyl group after polymerization and introducing an alkenyl group during polymerization. Methods can be broadly divided.

In the method of introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain or side chain may be used. An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having both an active group and an alkenyl group exhibiting reactivity.

Examples of the organic compound having both an active group and an alkenyl group reactive to the above functional group include C ₃ such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride and acrylic bromide. unsaturated fatty -C _20, acid halides, acid anhydrides or allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , non allyl bromo formate _{(CH 2 = CHCH 2 OCOBr)} C 3 -C 20 , such as Saturated aliphatic alcohol substituted carbonate halide, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1- Butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) ) Benzene, allyloxy (chloromethyl) benzene, allyl isocyanate, allyl glycidyl ether, and the like.

Further, there is a method of introducing an alkenyl group using a transesterification method. In this method, an alcohol residue in an ester portion of a polyester resin or an acrylic resin is transesterified with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst. The alkenyl group-containing alcohol and alkenyl group-containing phenol derivative used for exchange with the alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and at least one hydroxyl group. A catalyst may or may not be used, but if used, titanium-based and tin-based catalysts are preferred.

Examples of the compounds used in the above method include vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol and 6-heptene-1-ol. All, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glycerin diallyl ether, trimethylolpropane diallyl ether, Trimethylolethane diallyl ether, pentaerythritol triallyl ether, 1,2,6-hexanetriol diallyl ether, sorbitan diallyl ether,

Embedded image And the like. Among them, allyl alcohol, vinyl alcohol, 3-butene-1-
All, 2- (allyloxy) ethanol, and

Embedded image Is preferred.

Further, the esterification of the above-mentioned alcohol or phenol derivative such as an acetic acid ester with the ester portion of the polyester resin or the acrylic resin is transesterified with the use of a transesterification catalyst. There is also a method of introducing an alkenyl group by distilling a low molecular weight esterified product such as an acetate ester of the residue out of the system by devolatilization under reduced pressure or the like.

Further, methyl (meth)
After polymerization of acrylate or the like, an alkenyl group can be introduced into the terminal by a method of terminating the living terminal with a compound having an alkenyl group.

In the method of introducing an alkenyl group during the polymerization, for example, when the organic polymer skeleton of the component (A) used in the present invention is produced by a radical polymerization method, a radical such as allyl methacrylate or allyl acrylate is added to the molecule. By using a vinyl monomer having a low reactivity alkenyl group or a radical chain transfer agent having a low radical reactivity alkenyl group such as allyl mercaptan to introduce an alkenyl group into a side chain or a terminal of an organic polymer skeleton. Can be.

Specific examples of the component (A) having an alkenyl group introduced into a side chain or a terminal of the polymer skeleton include:

Embedded image (However, R ⁶ represents H or CH ₃ , R ²² ,
R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ^{27 each} represent C,
1 to 6 carbon atoms containing only H, N, O, S, and halogen
X and Y represent C, H, and C as constituent elements.
It represents a divalent substituent having 0 to 10 carbon atoms containing only N, O, S, and halogen, and n, m, and l represent integers of 1 to 300. ),

Embedded image

Embedded image (However, in the formulas (3) and (4), R ⁶ is H
Or CH ₃ , R ⁷ , R ⁸ , R ¹¹ , R ¹² , R
¹³ shows C, H, N, O, S, a divalent substituent of 0-6 carbon atoms containing a halogen only as an element, R ^9, R
¹⁰ , R ¹⁴ , R ¹⁵ and R ^{16 each} represent a monovalent substituent having 0 to 6 carbon atoms, and X and Y represent C, H, N, O,
S represents a divalent substituent having 0 to 10 carbon atoms containing only halogen, n, m, l, and s represent an integer of 1 to 300;
p and q show the integer of 0-3. In order to introduce an alkenyl group into a monomer skeleton of a phenol compound, a bisphenol compound, or the like, the alkenyl group may be introduced after the above-described polymerization.

Examples of the phenol compound into which the alkenyl group is introduced include phenol, cresol, xylenol, resorcin, catechol, pyrogallol and the like. Examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A.

Specific examples of the component (A) having an alkenyl group introduced into the monomer skeleton include:

Embedded image (However, R ⁶ represents H or CH ₃ , R ¹⁷ represents a divalent substituent having 0 to 6 carbon atoms containing only C, H, N, O, S, and halogen as constituent elements; ¹⁸ and R ^{19 each} represent a monovalent substituent having 0 to 10 carbon atoms, and X and Y each represent a divalent C0 to C10 containing only C, H, N, O, S, and halogen as constituent elements. And n and m each represent an integer of 0 to 4.).

As the component (A), carbon-
Such as butadiene, isoprene, decadiene, diallyl phthalate, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene having two or more carbon double bonds These low-molecular compounds can be used alone or in combination with other compounds. By using such a low molecular compound, the crosslink density of the foam can be increased.

The number of carbon-carbon double bonds in the organic compound (A) is preferably more than 1.0 on average per molecule, and more preferably 2 or more.
This is because, when the number of carbon-carbon double bonds in one molecule of the component (A) is 1 or less, the reaction with the component (B) results in only a graft structure and not a crosslinked structure.

The organic compound of component (A) must be fluid at a temperature of 100 ° C. or less so that it can be uniformly mixed with other components and a foam can be obtained by spraying or pouring. Is preferred. Its structure may be linear or branched, and the molecular weight is not particularly limited.
Any one of about 100,000 can be suitably used, and if it is an alkenyl group-containing organic polymer, it is 500 to 20,000.
00 is particularly preferred. When the molecular weight is less than 500, characteristics due to the use of an organic polymer such as imparting flexibility are hardly exhibited, and when the molecular weight exceeds 100,000, the effect of crosslinking by reaction between an alkenyl group and a SiH group tends to be hardly exhibited. is there.

Next, the compound having a SiH group (hydrosilyl group) as the component (B) will be described.

First, a polyorganohydrogensiloxane modified with a polyoxyalkylene group, which is used as an essential component in the component (B), will be described.

By containing a polyorganohydrogensiloxane modified with a polyoxyalkylene group, it is possible to obtain a foam having good foam-regulating properties, uniform and fine cells, and a high expansion ratio.

Specific examples of the polyorganohydrogensiloxane include a compound represented by the following formula (1) or (2).

[0058]

Embedded image (However, m ≧ 2, n, l, p ≧ 0, 10 ≦ (m + n +
l) × p ≦ 80, and R ¹ has a molecular weight of 100 to 10
000 polyoxyalkylene chain; R ² , R ³ ,
R ⁴ and R ⁵ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain one or more phenyl groups. )

Embedded image (However, m ≧ 2, n, l, p ≧ 0, 3 ≦ (m + n +
l) × p ≦ 20, and R ¹ has a molecular weight of 100 to 10
2,000 polyoxyalkylene chains, and R ² , R
³ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more phenyl groups. As a method for obtaining the polyorganohydrogensiloxane represented by the above formula (1) or (2), a terminal has a functional group capable of reacting with a SiH group such as a double bond (for example, an allyl group) or a hydroxyl group. Polyoxyalkylene compound, a method by the reaction of polyorganohydrogensiloxane, a method of synthesizing a polyorganohydrogensiloxane using a silicon compound having a polyoxyalkylene chain in advance, or the above-mentioned silicon compound and polyorganosiloxane Can be used.

More specifically, for example, the following equations (10) and (11):

Embedded image (However, m ≧ 2, l, p ≧ 0, 10 ≦ (m + 1) × p
≦ 80, and R ² , R ³ , R ⁴ , and R ⁵ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain one or more phenyl groups. ),

Embedded image (However, m ≧ 2, l, p ≧ 0, 3 ≦ (m + 1) × p ≦
R ² and R ³ are hydrogen or C 1-20
And may contain one or more phenyl groups. A) a chain or cyclic polyorganohydrogensiloxane represented by the formula: H ₂ C ＝ CHCH ₂ -[(PO) _n- (EO) _m ] _l-
OH H ₂ C = CHCH ₂ -[(PO) _n- (EO) _m ] _l-
OCH ₃ H ₂ C = CHCH ₂ -[(PO) _n- (EO) _m ] _{l-
OC 2 H 5 H 2 C =} CHCH 2 - [(PO) n - (EO) m] l -
OC ₃ H ₇ H ₂ C = CHCH ₂ -[(PO) _n- (EO) _m ] _{l-
OC 4 H 9 H 2 C =} CHCH 2 - [(PO) n - (EO) m] l -
_{OPh HO - [(PO) n} - (EO) m] l -CH 3 HO - [(PO) n - (EO) m] l -C 2 H 5 HO - [(PO) n - (EO) m] _{l -C 3 H 7 HO - [} (PO) n - (EO) m] l -C 4 H 9 HO - [(PO) n - (EO) m] l -Ph (1 ≦ (m + n) × l ≦ 80, m, n, l ≧ 0) or a chain or cyclic polyorganohydrogensiloxane represented by the above formulas (10) and (11);

Embedded image (However, 5 ≦ m ≦ 80, and R ¹ has a molecular weight of 10
Indicate 0 to 10,000 polyoxyalkylene chains. )
And

Embedded image (However, 3 ≦ m ≦ 20, and R ¹ has a molecular weight of 10
Indicate 0 to 10,000 polyoxyalkylene chains. ), Equilibration reaction and the like.

Here, in the polysiloxanes represented by the formulas (1) and (2), the ratio of the silicon atom to which the polyoxyalkylene group is bonded to all siloxane units, that is, ｛in the formulas (1) and (2) n / (m + n +
l)｝ × 100 (%) is called denaturation rate. In order to obtain sufficient foam controllability, the above modification rate is generally 5 to 90%, preferably 5 to 90%, although it depends on the composition and mixing ratio of other components.
~ 25% is particularly preferred. If the modification rate is lower than this, the compatibility with the component (A) is deteriorated, the foam-regulating property is reduced, the cells of the foam are not made fine, and in some cases, foaming occurs during foaming, and sufficient foaming occurs. Magnification may not be obtained.
Conversely, if the modification ratio is higher than this, the hydrosilyl group equivalent becomes large, and in order to obtain a foam using this compound alone as the component (B), a large amount of the component (B) is required. This is not preferable because only a low-foamed foam is obtained.

The structure of the polyoxyalkylene chain is as follows:
It is preferable that the ratio of oxyethylene units is large, and the ratio of oxyethylene units to all oxyalkylene units is 50 to 100% in terms of several units. If the ratio of the oxyalkylene units is smaller than this, sufficient foam control properties cannot be obtained. Although the molecular weight of the oxyalkylene chain is not particularly limited, the number average molecular weight is preferably 100 to 10,000, more preferably 100 to 3000, and 200 to 1
000 is particularly preferred. If the number average molecular weight is smaller than this, sufficient foam control properties cannot be obtained, and if the number average molecular weight is larger, the density of hydrosilyl groups decreases, so a large amount must be used to cure sufficiently in producing a foam. Therefore, it is not preferable because only a foam having a low expansion ratio can be obtained.

The organohydrogenpolysiloxane represented by the formulas (1) and (2) can be used in combination with another compound having a hydrosilyl group. The mixing ratio is not particularly limited, but it is desirable to add another compound to such an extent that the foaming behavior is not affected.

Specific examples of other compounds having a hydrosilyl group include linear and cyclic polyorganohydrogensiloxanes (including modified alcohols, olefins and styrenes) and the following formula (12). The organic compounds having a molecular weight of 30,000 or less and containing a hydrosilyl group are exemplified.

R ²⁸ Xa (12) (X represents a group containing at least one hydrosilyl group, R ²⁸ represents a monovalent to tetravalent organic group having 2 to 150 carbon atoms, and a represents 1 to 4 In the formula (12), X represents a group containing at least one hydrosilyl group, and if specifically exemplified, the following formulas (13) to (15) And the like, a hydrosilyl group derived from various polyvalent hydrogen siloxanes,

Embedded image (However, 1 ≦ (m + n) × l ≦ 10, n ≧ 1;
R ²⁹ represents any one of a methyl group, an ethyl group and a phenyl group, and Z represents C, H, N, O, S, S
i represents a divalent substituent having 0 to 10 carbon atoms containing only halogen. ),

Embedded image (However, in Expressions (14) and (15), 1 ≦
(M + p) × l + (n + q) × r ≦ 10, m + n ≧ 1,
l, p, q, r ≧ 0, R ²⁹ represents any one of a methyl group, an ethyl group and a phenyl group, and Z represents only C, H, N, O, S, Si or halogen as a constituent element And a divalent substituent having 0 to 10 carbon atoms. ), _{And, -SiH n (CH 3) 3} -n, -SiH n (C 2 H 5)
_{3-n, -SiH n (C} 6 H 5) 3-n ( provided that _{n = 1~3) -SiH 2 (C} 6 H 13) -Si (CH 3) 2 OSi (CH 3) 2 H

Embedded image And the like.

As the divalent substituent Z in the formulas (13) to (15),

Embedded image Is exemplified. Further, two or more of these divalent substituents may be connected by a covalent bond to form one divalent substituent Z.

R ²⁸ in the above formula (12) is not particularly limited as long as it is a monovalent to tetravalent organic group directly bonded to the above X via a covalent bond.

Embedded image

Embedded image

Embedded image (In the above formula, the wavy line in the compound having a bicyclo ring indicates that the compound may be either endo or exo). Among these,

Embedded image Is preferred.

The number of hydrosilyl groups in the component (B) in the present invention may be at least one on average in one molecule, but is preferably larger as long as compatibility is not impaired. When the component (A) and the component (B) of the present invention are cured by a hydrosilylation reaction, if the number of the hydrosilyl groups is less than 2, curing is slow, and poor curing often occurs. Further, since the component (B) and the component (C) of the present invention are dehydrocondensed and participate in foaming, the number of the hydrosilyl groups is determined by a desired foaming magnification, but generally 3 or more. It is preferred that

Next, the component (C) having an OH group will be described.

The type of the compound having an OH group used in the present invention is not particularly limited, but it is not the OH group-containing (poly) siloxane often used in the conventional silicone foam, but a siloxane bond which is considered to be a cause of repelling of the paint. Is not included in the molecular skeleton, and it is preferable to use one or both of an organic compound in which an OH group is directly bonded to a carbon atom and water, whereby an organic compound having a carbon-carbon double bond is used. The effect becomes more pronounced. O
Compounds in which the H group is directly bonded to a carbon atom include alcohols, carboxylic acids, and the like.

As alcohols, methanol, ethanol, n-propanol, iso-propanol, n
-Butanol, iso-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
Monohydric alcohols such as ethylene glycol monophenyl ether, ethylene glycol monoallyl ether and glycerin diallyl ether, ethylene glycol, propylene glycol, 1,4-butylene glycol,
1,3-butylene glycol, 2,3-butylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 1,9-nonamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol , Sucrose, polyalcohols such as glycerin monoallyl ether, polypropylene glycol, polyethylene glycol and copolymers thereof, and polyether polyols such as polytetramethylene glycol (such as sorbitol, sucrose, tetraethylenediamine, ethylenediamine, etc. (Including those containing three or more OH groups in the molecule), adipate polyol, polycaprolactone polyol, polycarbonate polyol Phenol polyols such as polyester polyols, epoxy-modified polyols, polyetherester polyols, benzylic ether-type phenol polyols, fluorine polyols such as Lumiflon (manufactured by Asahi Glass Co., Ltd.), polybutadiene polyols, hydrogenated polybutadiene polyols, castor oil-based polyols, and halogen-containing Flame-retardant polyol, phosphorus-containing flame-retardant polyol, phenol, cresol, xylenol, resorcin, catechol, pyrogallol, bisphenol A, bisphenol B, bisphenol S, compounds having a phenolic OH group, such as phenolic resin,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, Alonix 57 manufactured by Toa Gosei Chemical Industry Co., Ltd.
00, 4-hydroxystyrene, HE-10, HE-20, HP-10 and HP-20 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. (all acrylic acid ester oligomers having an OH group at the terminal), Nippon Oil & Fats Co., Ltd. Blenmer PP series (polypropylene glycol methacrylate), Blemmer PE series (polyethylene glycol monomethacrylate), Blemmer PEP series (polyethylene glycol polypropylene glycol methacrylate), Blemmer AP-400 (polypropylene glycol monoacrylate), Blemmer AE-
350 (polyethylene glycol monoacrylate),
Blenmer NKH-5050 (polypropylene glycol polytrimethylene monoacrylate) and Blenmer GLM (glycerol monomethacrylate); Group-containing vinyl monomers (these can also be used as a dual-purpose substance of component (A) and component (C)), obtained by copolymerization of the OH group-containing vinyl monomer with acrylic acid, methacrylic acid, derivatives thereof, and the like. Acrylic resin having an OH group,
In addition, a resin having an OH group such as an alkyd resin and an epoxy resin is exemplified.

Among these OH group-containing compounds, the coalescence of bubbles due to evaporation and vaporization due to heat generation during the curing reaction,
Alcohols having 3 or more carbon atoms are desirable because they do not adversely affect the enlargement, foam breakage, etc., and specifically, n-propanol, iso-propanol, n-butanol, i
Preferred are so-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and the like. Furthermore, n-propanol, n-butanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl are preferred from the viewpoint of ease of reaction with the Si-H group, no cross-linking even when dehydrocondensation proceeds, and of odor during handling. Primary alcohols such as ether and ethylene glycol monophenyl ether are particularly preferred.

On the other hand, carboxylic acids include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, hexanoic acid, 2-ethylhexanoic acid, malonic acid, succinic acid, adipic acid, meso-1,2 , 3,4-tetracarboxylic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. Among them, a monovalent carboxylic acid is preferable because of ease of reaction with Si-H groups and cross-linking does not occur even if dehydrocondensation proceeds, and 2-ethylhexanoic acid is particularly preferable from the viewpoint of odor during handling. preferable.

When the hydroxyl equivalent is increased, the volume of the OH group-containing compound to be added is increased, and the expansion ratio is not increased. Therefore, a compound having a hydroxyl equivalent of 1 to 33 mmol / g is preferable, and from the viewpoint of reactivity, 2.5 to 25 mmol is used. / G
Are more preferred.

It is also possible to use two or more OH compounds in combination for adjusting the foaming speed. Examples of combined use include primary alcohols such as n-propanol and iso-
A secondary alcohol such as propanol, a combination of a carboxylic acid and a primary alcohol, or a combination of a carboxylic acid and water is preferred. Further, for adjusting the curing time, polyvalent OH compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, glycerin and the like, ethylene glycol monoallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol Compounds having both a hydrosilylatable carbon-carbon double bond and an OH group in the molecule, such as diallyl ether, pentaerythritol triallyl ether, and undecylenic acid, can also be used.

When the component (C) having two or more OH groups in one molecule is used, the reaction between the components (B) and (C) generates hydrogen gas and forms a crosslinked structure. For this reason, it is possible to use a small amount for the purpose of adjusting the curing time, but it is not desirable to use a large amount since the curing occurs before sufficient foaming is performed. Further, a compound having a carbon-carbon double bond and an OH group in one molecule can also be used as a dual-purpose substance of the component (A) and the component (C).

The mixing ratio of the three components (A) to (C) is appropriately selected depending on the structure of each component, the desired expansion ratio, and the desired physical properties, and is not particularly limited. The mole number x of the SiH group of the component (B), the mole number y of the carbon-carbon double bond of the component (A), and the number of moles of O of the component (C).
The ratio of the molar number z of the H group to the sum is x: y + z = 30: 1.
１ ： 1: 30. More preferably,
x: y + z = 10: 1 to 1:10. If the molar ratio of the SiH groups exceeds x: y + z = 30: 1, the crosslinking density becomes low, sufficient mechanical strength cannot be obtained, and x: y + z = 1:
If it is less than 30, sufficient foaming and curing will not occur.

The ratio of the number of moles y of the carbon-carbon double bond of the component (A) to the number of moles z of the OH group of the component (C) is not particularly limited. Although it can be appropriately selected depending on the physical properties to be obtained, the skeleton of the component (A), and the type of the component (C), generally, y: z = 100:
1-1: 100 is preferable, and y: z = 10: 1 to 1: 2.
0 is more preferred.

In the present invention, a catalyst for the dehydrocondensation of the component (B) with the component (C) and the addition reaction (hydrosilylation reaction) between the component (A) and the component (B) are appropriately used. Can be.

Examples of the hydrosilylation catalyst include: platinum alone, alumina, silica, carbon black or the like with solid platinum supported thereon, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc .; -An olefin complex (for example, Pt (CH ₂ ＣＨCH ₂ ) ₂ (PP
_{h 3) 2, Pt (CH} 2 = CH 2) 2 Cl 2), Platinum -
Vinyl siloxane complex (for example, Pt _n (ViMe ₂ S
iOSiMe ₂ Vi) _n , Pt [(MeViSi
O) ₄ ] _m ), a platinum-phosphine complex (for example, Pt
(PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complex (for example, Pt [P (OPh) ₃ ] ₄ , Pt
[P (OBu) ₃ ] ₄ ) (where Me is a methyl group, Bu
Represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers. ), Dicarbonyldichloroplatinum, Karstedt's catalyst, and also Ashby U.S. Pat. No. 31,596.
No. 01 and 3159662, and a platinum-hydrocarbon complex, and Lamoree.
aux) U.S. Pat. No. 3,220,972. Further, the platinum chloride-olefin complexes described in Modic U.S. Pat. No. 3,516,946 are also useful in the present invention. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ ,
Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl
₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ ,
TiCl _{4 and the} like. Among these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited.
The range is preferably from 10 ^-1 to 10 ^-8 mol, more preferably from 10 ^-2 to 10 ^-6 mol, per 1 mol of the H group.

A phosphine compound and a phosphine complex can be used as a promoter together with the above catalyst. Examples of such a phosphine-based compound include triphenylphosphine, PMe ₃ , PEt ₃ , and PPr ₃ (where Pr represents a propyl group; the same applies hereinafter), P (n-
Bu) ₃ , P (cyclo-C ₆ H ₁₁ ) ₃ , P (p-C
_{6 H 4 Me) 3, P} (o-C 6 H 4 Me) but are not limited to such _3. Examples of the phosphine complex include Cr (CO) ₅ PPh ₃ and Cr (CO) ₄
(PPh ₃ ) ₂ (cis and trans isomers), Cr
(CO) ₃ (PPh ₃ ) ₃ (fac and mer isomers), Mo and V analogs of these Cr compounds, Fe
(CO) ₄ PPh ₃ , Fe (CO) ₃ (PPh ₃ ) ₂ ,
And Ru and Os analogs of these Fe compounds, C
oCl ₂ (PPh ₃ ), RhCl (PPh ₃ ) ₃ , Rh
Cl (CO) (PPh ₃ ) ₃ , IrCl (CO) (PP
h) ₂ , NiCl ₂ (PPh) ₂ , PdCl ₂ (PP
h) ₂ , PtCl ₂ (PPh) ₂ , and ClAu (P
Ph ₃ ). Further, metal complexes such as the above-mentioned metal complexes containing phosphines other than triphenylphosphine can also be effective cocatalysts. Further, P (OP
h) ₃ phosphite such as, complexes containing stibine, such as arsine and SBPH ₃ such as AsPh ₃ also may be effective cocatalysts.

[0082] The amount of co-catalyst is not particularly limited, the catalyst 1 mol, preferably ^10-2 to ² mols, more preferably from 10 ^-1 to 10 ¹ mol.

In the resin composition of the present invention, a foaming agent can be added as a component (D) in addition to the components (A) to (C) for the purpose of controlling foaming and improving the expansion ratio. . The foaming agent as the component (D) in the present invention is not particularly limited, and for example, can be selected from those usually used for organic foams such as polyurethane, phenol, polystyrene, and polyolefin. In order to produce a stable foam, a method in which a volatile compound is added to the composition in advance as a foaming agent and foaming is performed by heat generation or reduced pressure is preferred, and the boiling point is preferably 100 ° C. or lower, more preferably 50 ° C. or lower.

The type of the volatile compound is not particularly limited, but from the viewpoint of workability and safety, a compound selected from organic compounds such as hydrocarbons, chlorofluorocarbons and ethers, and compounds selected from carbon dioxide, nitrogen, air and the like, alone or in combination. It is preferable to use them.

Examples of the hydrocarbon include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,
Examples thereof include 2,3-dimethylbutane, cyclopentane, cyclobutane, cyclopentane, and cyclohexane.

As fluorocarbons, trichlorofluoromethane (R11), dichlorodifluoromethane (R1)
2), chlorotrifluoromethane (R13), bromotrifluoromethane (R13B1), tetrafluoromethane (R14), dichlorofluoromethane (R21), chlorodifluoromethane (R22), trifluoromethane (R23), difluoromethane (R32), Fluoromethane (R41), tetrachlorodifluoroethane (R1
12), trichlorotrifluoroethane (R113),
Dichlorotetrafluoroethane (R114), dibromotetrafluoroethane (R114B2), chloropentafluoroethane (R115), hexafluoroethane (R116), chlorotrifluoroethane (R12
3), tetrafluoroethane (R134a), dichlorofluoroethane (R141b), chlorodifluoroethane (R142b), difluoroethane (R152a), octafluoropropane (R218), dichloropentafluoropropane (R225), hexafluoropropane (R236ea), penta Fluoropropane (R245
fa), octafluorocyclobutane (RC318),
Hexafluorobutane (R356mffm), pentafluorobutane (R365mfc), decafluorohexane (R4310mee) and the like can be mentioned. Considering environmental issues, hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (CFC)
So-called alternative CFCs are preferred, and it is particularly preferred to use hydrofluorocarbons (HFCs). That is, tetrafluoroethane, difluoroethane, octafluoropropane, hexafluoropropane, pentafluoropropane, octafluorocyclobutane, hexafluorobutane, and pentafluorobutane are particularly excellent.

As ethers, dimethyl ether,
Diethyl ether, ethyl methyl ether, dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, 1,1-dimethylpropyl methyl ether, methylpentafluoroethyl ether, , 2,2-trifluoroethyl ether, methyl (trifluoromethyl) tetrafluoroethyl ether and the like.

As another foaming method, for example, NaH
CO ₃ , (NH ₄ ) ₂ CO ₃ , NH ₄ HCO ₃ , NH ₂
Inorganic foaming agents such as NO ₂ , Ca (N ₃ ) ₂ and NaBH _4, and organic materials such as azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate, dinitrosopentamethylenetetramine, and paratoluenesulfonyl hydrazide It is also possible to use a combination of a foaming agent, generation of carbon dioxide by a reaction between an isocyanate and an active hydrogen group-containing compound, mechanical stirring, and the like.

The resin composition of the present invention further comprises a filler,
Anti-aging agents, radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, foam stabilizers such as polydimethylsiloxane-polyalkylene oxide surfactants or organic surfactants (such as polyethylene glycol alkyl phenyl ether); Acids or basic compounds (additives for adjusting the reaction between SiH groups and OH groups, suppresses the condensation reaction with acids and accelerates with bases), storage stability improvers, ozone deterioration inhibitors, light stability Agents, thickeners, plasticizers, coupling agents, antioxidants, heat stabilizers, conductivity-imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metals A deactivator, a physical property modifier and the like can be added as long as the object and effects of the present invention are not impaired.

Specific examples of the above filler include, for example,
Glass fiber, carbon fiber, mica, graphite, diatomaceous earth, terra alba, fumed silica, precipitated silica, silicic anhydride, alumina, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, barium sulfate, quartz, aluminum Fine powder, flint powder, zinc powder, inorganic balloon, rubber granules, wood powder, phenol resin, melamine resin, vinyl chloride resin and the like can be mentioned.

As the above anti-aging agent, generally used anti-aging agents, for example, citric acid, phosphoric acid, sulfur-based anti-aging agents and the like are used.

Examples of the sulfur-based antioxidants include mercaptans, salts of mercaptans, sulfides including sulfide carboxylate esters, hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophos, and the like. Examples include fates, sulfonium compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides, and the like.

Examples of the above radical inhibitor include 2,2'-methylene-bis (4-methyl-6-t-butylphenol) and tetrakis (methylene-3 (3,5-
Phenolic radical inhibitors such as di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine,
Examples thereof include amine radical inhibitors such as N, N'-secondary butyl-p-phenylenediamine, phenothiazine, and N, N'-diphenyl-p-phenylenediamine.

As the above-mentioned ultraviolet absorber, for example, 2
(2′-Hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like.

As the above-mentioned adhesiveness improving agent, generally used adhesives, silane coupling agents such as aminosilane compounds and epoxysilane compounds, and other compounds can be used. Specific examples of such an adhesion improver include a phenol resin, an epoxy resin, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, a cumarone-indene resin, a rosin ester resin, Examples include terpene-phenol resins, α-methylstyrene-vinyltoluene copolymers, polyethylmethylstyrene, alkyl titanates, aromatic polyisocyanates, and the like.

Examples of the flame retardant include tetrabromobisphenol A, tetrabromobisphenol A epoxy,
Halogen-based agents such as decabromodiphenyl oxide,
Triethyl phosphate, tricresyl phosphate,
Tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl)
Examples include phosphorus-based flame retardants such as phosphate, ammonium polyphosphate, and red phosphorus, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, and antimony pentoxide. These flame retardants may be used alone or in combination.

Next, a method for producing the foam of the present invention will be described.

A foam is produced by mixing the foamable resin composition of the present invention, a catalyst, and, if necessary, an additive, followed by foaming and curing. The temperature for foam hardening is 100
° C or less is preferable, and considering application to in-situ foaming, it is more preferable to be close to normal temperature. At high temperatures exceeding 100 ° C,
The rate of the addition-type crosslinking (curing) reaction between the component (A) and the component (B) is too high, and it is difficult to balance foaming with hydrogen gas generated by the reaction between the component (B) and the component (C). .

In the present invention, the production of the foam is carried out by mixing the foamable resin composition of the present invention, the catalyst and, if necessary, the additives in an appropriate combination and mixing two or more liquids in advance. It is desirable to use a method in which separate mixtures are mixed immediately before use and directly applied to the surface of a substrate and foamed in situ, or a method in which a similar mixture is mixed immediately before use and foamed by injection. As a mixing method, a method such as hand mixing, an electric mixer, a static mixer, and collision mixing can be used. In particular, in the case of foaming in situ, it is preferable to use a static mixer or collision mixing.

The foaming resin composition of the present invention and the catalyst may be combined in the form of two or more separate mixtures in which additives are previously mixed as necessary, as follows. However, the combination is not limited to these as long as generation and hardening of hydrogen do not proceed before all the components are mixed. That is, (1)
A mixture of a part of the component (A) and the component (B);
(2) Two liquids consisting of a mixture of the component (A), the component (C) and the catalyst, and only the component (B). Or (3)
A mixture of the component (A) and the component (C) and a mixture of the component (B) and the catalyst, and the like.

The method of adding the component (D) is not particularly limited, and can be applied to any of the above methods.

The method for forming the foam is not particularly limited. For example, extrusion foaming, continuous foaming, cast molding, discontinuous molding, or in-situ foaming can be used to produce polyurethane foam, phenol foam, silicone foam, etc. Various foam molding methods used for the above can be used as appropriate.

Examples of the continuous foaming method include a slab foaming method in which foam is freely foamed on paper or a plastic film continuously fed on a belt conveyor, and molding with a face material such as paper, veneer plate, metal plate, and laminating. For example, a double conveyor method is used. The casting molding method is a method in which a foam having a desired shape is discharged and foamed, cured and cured to form a molded product conforming to the inner surface shape of the mold. The discontinuous molding method is used for molding a sandwich panel or the like. Examples of on-site construction methods include a one-part simple spray method, a two-part spray method, a two-part injection method, and a two-part coating method, and are mainly used for building insulation.

The expansion ratio of the foam in the present invention was expressed as (volume of foam) / ((volume of foam) − (volume of void in foam)). Although there is no particular limitation on the expansion ratio, it is preferably at least 2 times, particularly preferably at least 4 times, at which useful features due to the foam are remarkable.

As described above, the foamable resin composition of the present invention can be foamed in situ since it foams under heating at room temperature or at a relatively low temperature, and is free of isocyanate, has low toxicity, and has a low expansion ratio. By increasing the value, the price per unit volume can be reduced.

Further, according to the production method of the present invention characterized by using the foamable resin composition, the weather resistance, the coating property and the adhesion are good, and no harmful gas is generated during combustion. A foam having excellent characteristics is obtained.

Further, by selecting the composition of the component (A) (molecular weight between the skeleton and the cross-linking point) and the mixing ratio of each component, it is possible to produce from a hard foam to a soft foam, and the expansion ratio is from low to high. Can be set up to. Furthermore, it is possible to control the reaction rate of chemical foaming and crosslinking, and (B)
By using a compound having a specific structure as a component, a foam having a fine and uniform cell structure can be produced.

[0108]

EXAMPLES Examples and comparative examples of the present invention are shown below.

Synthesis Example 1 In a four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel, and a stirring motor, 114 g of bisphenol A, 145 g of potassium carbonate, 140 g of allyl bromide, and 250 g of acetone
Then, the mixture was stirred at 60 ° C. for 12 hours. This was allowed to stand, and the supernatant was taken, washed with an aqueous sodium hydroxide solution using a separating funnel, and then washed with water. After the oil layer was dried over sodium sulfate, the solvent was distilled off using an evaporator, and 126 g of a pale yellow liquid was obtained. This liquid
¹ H-NMR revealed that bisphenol A was an allylated bisphenol in which the OH group of the bisphenol A was allyl etherified. The yield was 82% and the purity was 95% or more.

Synthesis Example 2 The allylated bisphenol obtained in Synthesis Example 1 was heated at 180 ° C. for 3 hours while stirring under a nitrogen atmosphere.
A tan viscous liquid (A-1) was obtained. This is ¹
H-NMR measurement confirmed that the allyl group was C-allylated bisphenol in which Claisen rearrangement was performed.

Synthesis Example 3 ( Synthesis of O-allylated novolak type phenol resin) A novolak type phenol resin (PSM) was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a dropping funnel and a stirring motor.
4261, manufactured by Gunei Chemical Co., Ltd., OH content 9.71 mmo
1 / g) 36.9 g and acetone 160 ml were added, and 50 g of potassium carbonate was added with stirring. After dropping 52 g of allyl bromide little by little, the mixture was reacted at 55 ° C. for 6 hours. This was filtered, concentrated, washed in the order of alkali and acid, added with 7.4 g of aluminum silicate and stirred, then filtered and concentrated, and the unsaturated group content measured by iodine value was 7. 40 g of 3 mmol / g product were obtained. This product was confirmed by ¹ H-NMR measurement to be an O-allylated novolak type phenol resin (A-2, allyl ether type) in which the hydroxyl group was allylated.

Synthesis Example 4 ( Synthesis of C-allylated novolak type phenol resin) 40 g of the allylated novolak type phenol resin (A-2) obtained in Synthesis Example 3 was stirred under a nitrogen atmosphere for 180 g.
Heating at 3 ° C. for 3 hours gave 40 g of a rearranged product having an unsaturated group content of 7.3 mmol / g as measured by iodine value.
The product was confirmed by ¹ H-NMR measurement to be a C-allylated novolak type phenol resin (A-3, allylphenol type) in which the allyl group was Claisen rearranged.

Synthesis Example 5 In a 1-liter four-necked flask, a stirring rod, a dropping funnel,
A cooling tube equipped with a three-way cock at the top and a thermometer were set. In this flask, 120 g of methyl hydrogen polysiloxane (KF-99, Shin-Etsu Chemical Co., Ltd., 2.0 mol), 241 μl of a xylene solution of a platinum-vinylsiloxane complex (2.0 × 10 ⁻² mm in terms of platinum atom)
ol) and 120 ml of toluene. 80 ° C
From the dropping funnel, 70 g of an ethylene oxide polymer (number average molecular weight 350) modified with a methyl group at one end and an allyl group at the other end.
(20 mol) dissolved in 70 ml of toluene was added dropwise over 0.5 hour, and after completion, the mixture was stirred at 80 ° C. for 2 hours.

After confirming that the peak of the vinyl group had disappeared by ¹ H-NMR, the reaction mixture was cooled, 10 g of activated carbon was added, and the mixture was stirred at room temperature for 1 hour. The mixture was filtered, and the filtrate was concentrated to obtain a methylhydrogenpolysiloxane (B
-1) was obtained as a viscous liquid. S of this polysiloxane
The measured iH value was 9.1 mmol / g.

Synthetic Example 6 The same operation as in Synthetic Example 5 was carried out using 120 g of methyl hydrogen polysiloxane and 195 g (0.50 mol of allyl group) of an ethylene oxide polymer to obtain methyl hydrogen modified with a polyoxyalkylene group. Siloxane (B-2) was obtained as a viscous liquid. The SiH value was 4.9 mmol / g.

Synthesis Example 7 The same operation as in Synthesis Example 5 was carried out using 120 g of methyl hydrogen polysiloxane and 28 g of ethylene oxide polymer (0.08 mol of allyl group) to obtain methyl hydrogen modified with a polyoxyalkylene group. Siloxane (B-3) was obtained as a viscous liquid. SiH value is 1
0.0 mmol / g.

Synthetic Example 8 According to Synthetic Example 5, 120 g of methylhydrogenpolysiloxane, 110 g of ethylene oxide polymer (number average molecular weight 550) modified with a methyl group at one end and an allyl group at the other end, respectively. Group 0.2mol)
To obtain methylhydrogensiloxane (B-4) modified with a polyoxyalkylene group as a viscous liquid. The SiH value was 7.4 mmol / g.

Synthesis Example 9 The same operation as in Synthesis Example 5 was carried out except that 120 g of methyl hydrogen polysiloxane and 52 g (0.5 mol) of styrene were used to modify methyl hydrogen polysiloxane (B-5) modified with styrene. Was obtained as a viscous liquid. The SiH value was 7.6 mmol / g.

Example 1 The C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl group) of the modified methyl hydrogen polysiloxane (B
-1) 11.0 g (100 mmol of SiH group), water 0.1%.
54 g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. To this mixture was added a platinum-vinylsiloxane xylene solution (1.9% by weight of platinum atom) 0.60.
g was added, stirred, and poured into a rectangular parallelepiped of known volume. 25
After standing at 10 ° C. for 10 minutes, a rigid foam was obtained. The obtained foam was cut by the upper part of the container, the weight was measured, the density was obtained, and the expansion ratio was obtained from the density before foaming obtained before addition of the catalyst. Further, when the shape of the cell was observed on the cut surface using an optical microscope, it was found that most of the cells had a uniform structure with a diameter of 0.3 to 0.7 mm.

Example 2 C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl groups) of the modified methyl hydrogen polysiloxane (B
-2) 20.4 g (100 mmol of SiH group), water 0.
54 g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. 0.60 g of a platinum catalyst solution was added to this mixture in the same manner as in Example 1 to obtain a rigid foam.
The expansion ratio of this foam was 18 times.

Comparative Example 1 The C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl group) of the modified methyl hydrogen polysiloxane (B
-3) 10.0 g (100 mmol of SiH groups), water 0.1 g.
54 g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. To this mixture, 0.60 g of a platinum catalyst solution was added in the same manner as in Example 1. The expansion ratio of the foam was 5 times, and the cells had an uneven structure with a diameter of 0.5 to 3 mm.

Comparative Example 2 The C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl group), methyl hydrogen polysiloxane (Shin-Etsu Chemical Co., Ltd., KF-9)
9) 6.0 g (100 mmol of SiH group), water 0.54
g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. To this mixture, 0.60 g of a platinum catalyst solution was added in the same manner as in Example 1. The expansion ratio of the foam is 5
The cells had a non-uniform structure with a diameter of 0.5 to 3 mm.

Example 3 C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl group) of the modified methyl hydrogen polysiloxane (B
-4) 13.5 g (100 mmol of SiH group), water 0.1%.
54 g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. 0.60 g of a platinum catalyst solution was added to this mixture in the same manner as in Example 1 to obtain a rigid foam.
The expansion ratio of the foam was 22 times.

Example 4 C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl group) of the modified methyl hydrogen polysiloxane (B
-1) 5.5 g (50 mmol of SiH groups) of the modified methyl hydrogen polysiloxane (B
-5) 6.6 g (SiH group 50 mmol), water 0.54
g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. 0.60 g of a platinum catalyst solution was added to this mixture in the same manner as in Example 1 to obtain a rigid foam. The expansion ratio of the foam was 22 times.

Comparative Example 3 The C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl groups) of the modified methyl hydrogen polysiloxane (B
-5) 13.2 g (100 mmol of SiH group), water 0.1%.
54 g, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. To this mixture, 0.60 g of a platinum catalyst solution was added in the same manner as in Example 1. The expansion ratio of the foam was 5 times, and the cells had an uneven structure with a diameter of 0.3 to 5 mm.

Example 5 9.6 g (70 mmol of vinyl group) of the O-allylated novolak phenol (A-2) produced in Synthesis Example 3 and the modified methyl hydrogen polysiloxane (B-1) 11 produced in Synthesis Example 5 2.0 g (100 mmol of SiH groups), 0.54 g of water, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution of triphenylphosphine (1% by weight).
Was stirred and mixed. 0.60 g of a platinum catalyst solution was added to this mixture in the same manner as in Example 1 to obtain a rigid foam. The expansion ratio of the foam was 15 times.

Example 6 9.6 g (70 mmol of vinyl group) of C-allylated novolak phenol (A-3) produced in Synthesis Example 4 and modified methyl hydrogen polysiloxane (B-1) 11 produced in Synthesis Example 5 2.0 g (100 mmol of SiH groups), 0.54 g of water, 2.2 g of 2-ethylhexanoic acid, and 0.19 g of a xylene solution of triphenylphosphine (1% by weight).
Was stirred and mixed. 0.60 g of a platinum catalyst solution was added to this mixture in the same manner as in Example 1 to obtain a rigid foam. The expansion ratio of the foam was 15 times.

Example 7 20.4 g (70 mmol of vinyl group) of a phthalic anhydride / diethylene glycol copolymer (A-4) modified with an allyl alcohol at the end, and the modified methyl hydrogen polysiloxane (B -1) 11.0g
(100 mmol of SiH group), 0.54 g of water, 1.0 g of 1-propanol, and 0.19 g of a xylene solution of triphenylphosphine (1% by weight) were mixed with stirring. The platinum catalyst solution 0.60 was added to this mixture in the same manner as in Example 1.
g was added to obtain a rigid foam. The expansion ratio of the foam is 1
It was 0 times.

Example 8 The phthalic anhydride / diethylene glycol copolymer (A-4) in Example 7 was replaced with 100.5 g (70 mmol of vinyl group) of polypropylene oxide (A-5) whose terminal was blocked with allyl ether. Except for the above, the same operation was performed to obtain a foam having an expansion ratio of 10 times.

Comparative Example 4 A two-pack silicone RTV foam (manufactured by Dow Corning Toray Silicone Co., Ltd., SEF-10) was prepared according to the instruction manual.

Example 9 The C-allylated bisphenol (A-
1) 10.8 g (70 mmol of vinyl group) of the modified methyl hydrogen polysiloxane (B
-1) 11.0 g (100 mmol of SiH groups), 0.6 g of n-propanol, 1.5 g of n-butane, and 0.19 g of a xylene solution (1% by weight) of triphenylphosphine were stirred and mixed. To this mixture, a xylene solution of platinum-vinylsiloxane (1.9% by weight of platinum atom) 0.6
As a result of adding 0 g and stirring, a good rigid foam having an expansion ratio of 25 times and having no cell roughness was obtained.

Example 10 The same procedure as in Example 9 was repeated, except that 1.7 g of pentafluoropropane (R245fa) was used instead of n-butane. I got

Example 11 C-allylated bisphenol (A-
1) 0.15 g of a platinum-vinylsiloxane xylene solution (1.9% by weight of platinum atom) in 10.8 g, 0.6 g of n-propanol, and tetrafluoroethane (R134a)
When a composition obtained by mixing 2.0 g in an autoclave and 10.6 g of the modified methyl hydrogen polysiloxane (B-1) produced in Synthesis Example 5 were discharged while being mixed, the mixture was foamed with heat generation, and the expansion ratio was 20. A doubled foam was obtained.

Example 12 C-allylated bisphenol (A-
1) A composition in which 0.1 g of a xylene solution of platinum-vinylsiloxane (1.9% by weight of platinum atom) was stirred in 15.4 g and 0.2 g of water was placed in a 100 mL stainless steel autoclave, and the mixture was stirred while being stirred. 10kgf / with carbon
The pressure was increased to cm ² (Solution A). Modified methyl hydrogen polysiloxane (B-1) 11.0 produced in Synthesis Example 5
g into another autoclave and add 1 g
The pressure was increased to 0 kgf / cm ² (Solution B). As a result of gradually discharging the liquid A and the liquid B while controlling the temperature with a heater, a foam having an expansion ratio of 10 times was obtained.

Table 1 shows the characteristic values of the foams obtained in Examples 1 to 12 and Comparative Examples 1 to 4.

The methods for evaluating foam control, coating properties and adhesiveness are as follows.

(1) Foam Controlling The foam was evaluated by visual observation. A sample in which no cell roughness was observed was evaluated as ○, and a sample in which cell roughness was observed was evaluated as ×.

(2) Coatability Three types of water-based acrylic paints were applied to the surface of the foam sample at room temperature, air-dried, and the state of the paint film was visually judged as follows.

・: Coating film formed, ×: paint was repelled.

(3) Adhesiveness with Adhesive Two-part epoxy adhesive (Cemedine 3000 Gold, manufactured by Cemedine Co., Ltd.) was applied to an aluminum test piece, and then adhered to the surface of the foam sample, and cured at room temperature for 1 hour. After doing
It was peeled off by hand and the peeled state was visually observed.

[0141]

[Table 1]

[Table 2]

[Table 3]

[0142]

According to the foamable resin composition of the present invention as set forth in claims 1 to 11, paintability, adhesiveness and the like are good.
A hard, semi-rigid or soft foam having good foam-regulating properties and a high expansion ratio can be obtained under heating at ordinary temperature or relatively low temperature. Therefore, in-situ foaming becomes possible, and the price per unit volume can be reduced by increasing the foaming ratio.

In particular, by selecting the composition of the component (A) (molecular weight between the skeleton and the cross-linking point), a hard foam to a soft foam can be obtained, and the expansion ratio can be adjusted from a low ratio to a high ratio.
By selecting the component (B), a foam regulating property is improved, a foam having fine cells and a high expansion ratio can be obtained, and a uniform and fine foam can be obtained by controlling the reaction rate of foaming and crosslinking. Since a cell structure can be obtained, it can be widely applied to various uses.

The foamable resin compositions of the present invention do not contain isocyanate and have low toxicity.

The foam of claim 13 obtained from the foamable resin composition is hard, semi-hard, or soft, and has good coatability and adhesiveness.

(1) The foamable resin composition according to (1).
According to the foam production methods 2, 14, and 15, a desired foam can be obtained under heating at room temperature or at a relatively low temperature, and so-called in-situ foaming, which has conventionally been difficult, is facilitated.

Claims (15)

[Claims] 1. A compound comprising (A) an organic compound having a carbon-carbon double bond and not containing a siloxane unit in a molecular skeleton, (B) a compound having SiH, and (C) a compound having an OH group, A foamable resin composition comprising, as at least a part of the component (B), a polyorganohydrogensiloxane modified with a polyoxyalkylene chain. 2. The polyorganohydrogensiloxane contained as at least a part of the component (B) has a structure represented by the following formula (1) or (2). 2. The foamable resin composition according to 1. Embedded image (However, m ≧ 2, n, l, p ≧ 0, 10 ≦ (m + n +
l) × p ≦ 80, and R ¹ has a molecular weight of 100 to 10
000 polyoxyalkylene chain; R ² , R ³ ,
R ⁴ and R ⁵ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain one or more phenyl groups. ) (However, m ≧ 2, n, l, p ≧ 0, 3 ≦ (m + n +
l) × p ≦ 20, and R ¹ has a molecular weight of 100 to 10
2,000 polyoxyalkylene chains, and R ² , R
³ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more phenyl groups. ) 3. The polyorganohydrogensiloxane of the formula (1) or (2), wherein R ¹ mainly comprises oxyethylene units.
3. The foamable resin composition according to item 1. 4. The method according to claim 1, wherein the molecular skeleton of the organic compound of the component (A) comprises only one or more of carbon, oxygen, hydrogen, nitrogen, sulfur and halogen. The foamable resin composition according to any one of claims 1 to 3. 5. The foamable resin according to claim 1, wherein the molecular skeleton of the organic compound as the component (A) is a polyether-based organic polymer skeleton. Composition. 6. The foamable resin composition according to claim 1, wherein the molecular skeleton of the organic compound as the component (A) is a polyester-based organic polymer skeleton. Stuff. 7. The method according to claim 1, wherein the organic compound as the component (A) has a structure of one or more of the following formulas (3) to (5) as a molecular skeleton. 4. The foamable resin composition according to any one of items 3 to 3. Embedded image Embedded image Embedded image (However, in the formulas (3) to (5), R ⁶ represents H or CH ³ , and R ⁷ , R ⁸ , R ¹¹ , R ¹² , R ¹³ , R
¹⁷ shows C, H, N, O, S, a divalent substituent of 0-6 carbon atoms containing a halogen only as an element, R ^9, R
¹⁰ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁸ and R ^{19 each} represent a monovalent substituent having 0 to 6 carbon atoms, and X and Y represent C,
Containing only H, N, O, S, halogen, carbon number 0-10
Represents a divalent substituent. In the formulas (3) and (4), n, m, l, and s represent integers of 1 to 300,
p and q each represent an integer of 0 to 3, and in the formula (5),
n and m show the integer of 0-4. ) 8. The organic compound according to claim 1, wherein the number of carbon-carbon double bonds in the organic compound of component (A) is at least two per molecule on average. The foamable resin composition as described in the above. 9. The compound according to claim 1, wherein the compound having an OH group as the component (C) is an organic compound in which the OH group is directly bonded to a carbon atom and / or water. Item 2. The foamable resin composition according to item 1. 10. The compound according to claim 1, wherein the compound having an OH group as the component (C) is at least one selected from alcohols, carboxylic acids, and water. Item 2. The foamable resin composition according to item 1. 11. In addition to the components (A) to (C), (D)
The foamable resin composition according to any one of claims 1 to 10, wherein a foaming agent is added as a component. 12. A method for producing a foam, comprising foaming and curing the foamable resin composition according to any one of claims 1 to 11 at a temperature of 100 ° C. or less. 13. A foam obtained by foam-curing the foamable resin composition according to claim 1 at a temperature of 100 ° C. or lower. 14. The foamable resin composition according to any one of claims 1 to 11, wherein the components (A) to (C) or (A) to
(D) A method for producing a foam, comprising mixing the components immediately before use, applying the mixture directly to the surface of the substrate, and foaming the mixture in situ. (15) The foamable resin composition according to any one of (1) to (11), wherein the components (A) to (C) or (A) to
(D) A method for producing a foam, comprising mixing the components immediately before use and injecting and foaming.