JP2012122021A - Foamable liquid resin composition and foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified silicone resin foam suppressed in change of physical properties with time and in residual compression strain and excellent in tactile sensation and flexibility.SOLUTION: The resin foam having the properties is obtained by curing and foaming a foamable liquid resin composition which is composed of a curing agent (A) having hydrosilyl of <500 g/mol functional group equivalent, a polymer (B) having at least one alkenyl in a molecular chain and a main chain constituted of a recurring unit composed of an oxyalkylene-based unit, a hydrosilylation catalyst (C), a foaming agent (D) and a specific lubricant (E), and whose hydrosilyl content in the foamable liquid resin composition is ≥0.5 mol and ≤10 mol per mol of alkenyl.

Description

  The present invention relates to a foamable liquid resin composition and a foam comprising a modified silicone resin.

  A foam using a modified silicone resin has been proposed as a soft foam having good tactile sensation and excellent flexibility (see, for example, Patent Document 1). The foam using the modified silicone resin has better tactile sensation than the foam made of polyurethane, which is a conventional soft foam, and has excellent flexibility such as low hardness and low rebound resilience, and toxicity. Therefore, it is suitable as a material for soundproofing materials, vibration damping materials, cushioning materials and the like.

However, further improvements are desired for improvements in tactile sensation, changes in tactile sensation and flexibility over time, and a tendency to increase compression residual strain.
On the other hand, as a foam excellent in compression residual strain resistance, a crosslinked foam made of an organic polymer having a vinyl group and a SiH group-containing compound has been proposed. (For example, refer to Patent Document 2) However, the expansion ratio is not large, and the hardness of the foam is high, and it is difficult to say that the feel is excellent.

International Publication No. 2008/117734 JP 2007-177082 A

  The inventors of the present invention provide a resin composition and a foam, which are modified silicone resin foams, in which changes in physical properties and compressive residual strain over time are suppressed, and the modified silicone resin foam has excellent tactile sensation and flexibility. There is.

  The present invention has the following configuration.

1). A hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol,
A polymer (B) having at least one alkenyl group in the molecular chain, wherein the repeating unit constituting the main chain is an oxyalkylene-based unit;
Hydrosilylation catalyst (C),
Foaming agent (D) and
A foamable liquid resin composition comprising a reactive lubricant (E) having a functional group equivalent of 500 g / mol to 8000 g / mol,
A foamable liquid resin composition having a hydrosilyl group content in the foamable resin composition of 0.5 to 10 moles per mole of alkenyl groups.

  2). The foamable liquid resin composition according to 1), wherein the reactive lubricant (E) is an organohydrogenpolysiloxane.

  3). The foamable liquid resin composition according to 1) or 2), wherein the polymer (B) has a number average molecular weight of 15000 or more and 50000 or less.

  4). The foamable liquid resin composition according to any one of 1) to 3), wherein the repeating unit constituting the main chain of the polymer (B) is oxypropylene.

  5). The foamable liquid resin composition according to any one of 1) to 4), wherein the foaming agent (D) is a chemical foaming agent that decomposes by heating to generate an inorganic gas such as carbon dioxide gas or nitrogen gas.

6). A hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol,
A polymer (B) having at least one alkenyl group in the molecular chain, wherein the repeating unit constituting the main chain is an oxyalkylene-based unit;
Hydrosilylation catalyst (C),
Foaming agent (D) and
Lubricant (E)
A foam formed by foaming the foamable liquid resin composition according to any one of 1) to 5).

7). The modified silicone foam according to 6), wherein the density is 30 kg / m ³ or more and 300 kg / m ³ or less.

  8). The foamable liquid resin composition according to 6) or 7), wherein the compressive residual strain is 10% or less when compressed 75% under the condition of 40 ° C. for 8 hours.

  9). Hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol, a polymer having at least one alkenyl group in the molecular chain and a repeating unit constituting the main chain consisting of an oxyalkylene unit (B ), A hydrosilylation catalyst (C), a foaming agent (D), and a reactive lubricant (E), the foamable liquid resin composition is foamed. The manufacturing method of the foam of description.

  10). 9. The method for producing a foam according to 9), wherein the foamable liquid resin composition is cured and foamed at a temperature of 40 ° C. or higher and 150 ° C. or lower.

  The modified silicone resin foam obtained from the foamable liquid resin composition of the present invention is less susceptible to a curing reaction (crosslinking) after the foam is produced, and suppresses deterioration in touch and flexibility over time and compression residual strain. Can do. In addition, since the foam has excellent tactile sensation and flexibility, it can be suitably used for applications such as vehicles, bedding / furniture, various equipment, building materials, packaging materials, and medical materials as soundproofing materials, vibration damping materials, and cushioning materials.

  The modified silicone resin constituting the foamable liquid resin composition of the present invention has a hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol, has at least one alkenyl group in the molecular chain, Polymer (B) in which repeating unit constituting chain is oxyalkylene unit, hydrosilylation catalyst (C), blowing agent (D), and reactive lubricant having functional group equivalent of 500 g / mol or more and 8000 g / mol or less A foamable liquid resin composition comprising (E), wherein the foamable liquid resin composition has a hydrosilyl group content of 0.5 mol or more and 10 mol or less per mol of alkenyl groups. It is a foam formed by curing and foaming.

-About hardening | curing agent (A) Since the hydrosilyl group hardening | curing agent (A) in which functional group equivalent in this invention is less than 500 g / mol has a hydrosilyl group in a molecular chain, it has at least 1 alkenyl group in a molecular chain. And the repeating unit constituting the main chain reacts with an alkenyl group present in the molecular chain of the polymer (B) comprising an oxyalkylene-based unit (hydrosilylation reaction) to be cured. The functional group equivalent of the hydrosilyl group in the curing agent (A) is preferably less than 500 g / mol, more preferably less than 400 g / mo, and still more preferably less than 300 g / mol. In addition, the functional group equivalent in this invention means what remove | divided the weight of 1 mol of molecules by the number of moles of the functional group in 1 mol of molecules.

  When the functional group equivalent is 500 g / mol or more, that is, when the molecular weight of the curing agent (A) is high or the number of functional groups is small, the curing rate when the liquid resin composition of the present invention is cured by a hydrosilylation reaction is slow. Thus, the balance between foaming and curing cannot be achieved, resulting in a defective structure. Although there is no restriction | limiting in particular as a lower limit of the functional group equivalent of a hardening | curing agent (A), From stability of a hardening | curing agent (A), ie, stability of a liquid resin composition, etc., 50 g / mol or more, Furthermore, 100 g / mol. The above is preferable.

  The number average molecular weight Mn of the curing agent (A) in the present invention is preferably 30000 as the upper limit, more preferably 20000, and more preferably 15000 or less from the viewpoint of reactivity with the polymer (B), dispersibility, workability and the like. More preferably. In consideration of compatibility and reactivity with the polymer (B), the number average molecular weight Mn of the curing agent (A) is particularly preferably from 300 to 10,000. The number average molecular weight Mn can be measured by various methods, but is easily measured by gel permeation chromatography (GPC).

  The number of functional groups of the hydrosilyl group of the curing agent (A) in the present invention is not particularly limited as long as the functional group equivalent is less than 500 g / mol, but alkenyl present in the molecular chain of the polymer (B). In order to cure by reacting with a group, those having at least 2 are preferred, those having 3 or more are more preferred, and those having 4 or more are particularly preferred. Further, when the number of functional groups of the hydrosilyl group is increased, the stability of the curing agent (A), that is, the stability of the foamable liquid resin composition tends to be deteriorated. 60 or less is particularly preferable.

In the present invention, the number of functional groups of the hydrosilyl group can also be referred to as the number of H atoms directly bonded to Si atoms. For example, in the case of SiH ₂ , the number of functional groups of the hydrosilyl group is two. When the number of H atoms bonded to one Si atom is one, the curability is improved, and it is also preferable from the viewpoint of flexibility.

  If the structure of the curing agent (A) in the present invention is a compound having a functional group equivalent of 500 g / mol or less and containing a hydrosilyl group in the molecular chain, even if the hydrosilyl group is in the main chain of the molecule, Even if it exists, there is no restriction | limiting in particular and a molecular chain also does not specifically limit, but organohydrogenpolysiloxane is preferable from a viewpoint of the availability of a raw material and a reactivity.

  In the organohydrogenpolysiloxane, the substituted or unsubstituted monovalent hydrocarbon group bonded to the Si atom is preferably an alkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, and decyl group. It is done. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.

  Examples of the organohydrogenpolysiloxane include trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, and trimethylsiloxy group-blocked methylhydrogensiloxane at both ends. -A diphenylsiloxane copolymer, a trimethylsiloxy group-blocked methyl hydrogen siloxane, a diphenylsiloxane, a dimethylsiloxane copolymer, etc. are mentioned.

  A hardening | curing agent (A) can be synthesize | combined by a well-known method, and what is marketed can use a commercial item as it is. Examples of commercially available organohydrogenpolysiloxanes having a functional group equivalent of less than 500 g / mol include KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent of 60 g / mol), KF-9901 (Shin-Etsu Chemical Co., Ltd.) ), Functional group equivalent 140 g / mol), HMS-151 (manufactured by Gelest, functional group equivalent 490 g / mol), HMS-301 (manufactured by Gelest, functional group equivalent 245 g / mol), HMS-991 (manufactured by Gelest) , Functional group equivalent 67 g / mol), SH1107 (manufactured by Toray Dow Corning Co., Ltd.), TSF484 (manufactured by Momentive Performance Materials), H-Siloxane (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and the like.

  In addition, in order to ensure compatibility with the polymer (B) and to adjust the amount of hydrosilyl group, organohydrogenpolysiloxane is changed to α-olefin, styrene, α-methylstyrene, allyl alkyl ether, allyl alkyl ester, allyl phenyl. Examples thereof include compounds modified with ether, allyl phenyl ester or the like. These may be used alone or in combination of two or more.

-About polymer (B) The polymer (B) in this invention is a polymer which has at least 1 alkenyl group in a molecular chain, and the repeating unit which comprises a principal chain consists of an oxyalkylene type unit. The alkenyl group is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active for hydrosilylation reaction. The alkenyl group is preferably an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, more preferably 2 to 4 carbon atoms, preferably a ring having 3 to 20 carbon atoms, more preferably 3 to 6 carbon atoms. A formula unsaturated hydrocarbon group and a (meth) acryl group are mentioned. Specific examples include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a methacryl group.

  The polymer (B) is a component that is cured by a hydrosilylation reaction with the curing agent (A). Since the polymer (B) has at least one alkenyl group in the molecular chain, the hydrosilylation reaction takes place and the polymer is cured. To do. The number of functional groups of the alkenyl group contained in the polymer (B) is at least one from the viewpoint of hydrosilylation reaction with the curing agent (A), but from the viewpoint of curability and flexibility, the main chain or branched It is preferable that alkenyl groups exist at both ends of the molecular chain. The bonding mode of the alkenyl group to the polyoxyalkylene polymer is not particularly limited, and examples thereof include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond.

The polymer (B) in the present invention is produced by polymerizing a compound having two or more active hydrogens as a starting material for forming the main chain because the repeating unit constituting the main chain is an oxyalkylene unit. be able to. For example, the polymer (B) can be produced by polymerizing a C _{2 to} C ₄ alkylene oxide using ethylene glycol, propylene glycol, a bisphenol compound, glycerin, trimethylolpropane, pentaerythritol, or the like.

  Specific examples of the main chain of the polymer (B) in the present invention include, for example, polyethylene oxide, polypropylene oxide, polybutylene oxide; two or more random or block copolymers selected from ethylene oxide, propylene oxide, and butylene oxide. , Etc. From the viewpoints of flexibility and touch, the repeating unit of the main chain is more preferably polypropylene oxide.

  The structure of the polymer (B) in the present invention may be linear or may have a branched structure in a range where the branching is smaller than the molecular weight of the main chain. It is preferable from the viewpoint of flexibility.

  The method for producing the polymer (B) is not particularly limited, and examples thereof include a method of introducing an alkenyl group after obtaining a polyoxyalkylene polymer. In this case, various known production methods can be applied to the oxyalkylene polymer, and a commercially available polyoxyalkylene polymer may be used. In addition, a method of introducing an alkenyl group into a polyoxyalkylene polymer is also known. For example, a monomer having an alkenyl group (eg, allyl glycidyl ether) and a monomer for synthesizing a polyoxyalkylene polymer are copolymerized. Or a functional group having reactivity to the functional group in a polyoxyalkylene polymer in which a functional group (eg, hydroxyl group, alkoxide group) has been introduced into a desired portion (end of main chain, etc.) in advance. And a method of reacting a compound having both a group and an alkenyl group (eg, acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride, etc.).

  As for the molecular weight of the polymer (B) in the present invention, the number average molecular weight Mn is preferably 15000 or more, and more preferably 17000 or more, from the viewpoint of balance between flexibility, touch and reactivity. The upper limit of the number average molecular weight Mn is not particularly limited, but is preferably 50000 or less, more preferably 45000 or less, and further preferably 40000 or less.

  In the present invention, the content of the curing agent (A) and the polymer (B) is such that the hydrosilyl group content in the curing agent (A) is the alkenyl group in the polymer (B) from the viewpoints of touch and flexibility. It is preferable to mix | blend so that it may become 0.5 mol or more and 10 mol or less per mol, 0.5 mol or more and 7.5 mol or less are preferable, and it mix | blends so that it may become 0.5 mol or more and 5.0 mol or less. It is more preferable.

  When the hydrosilyl group content is low, the curing rate when the foamable liquid resin composition of the present invention is cured by the hydrosilylation reaction is slowed, and the balance between foaming and curing cannot be achieved, resulting in a defective structure. In addition, when the hydrosilyl group content increases, a large amount of hydrosilyl groups are likely to remain in the foam even after curing, and the curing reaction (crosslinking) proceeds due to the influence of temperature and the like even after forming the product form. Tend to. For this reason, it becomes a cause of deterioration of tactile sensation and flexibility over time and compression residual strain.

-About hydrosilylation catalyst (C) As long as it can be used as a hydrosilylation catalyst as a hydrosilylation catalyst (C) in this invention, there is no restriction | limiting in particular, Arbitrary things can be used. Specific examples of the hydrosilylation catalyst (C) include platinum carriers; alumina, silica, carbon black and other carriers supported on solid platinum; chloroplatinic acid; complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc. Platinum-olefin complexes and platinum-vinylsiloxane complexes; platinum-phosphine complexes; platinum-phosphite complexes; dicarbonyldichloroplatinum and the like.

The content of the hydrosilylation catalyst (C) in the present invention is preferably from 10 ⁻⁸ mol to 10 ⁻¹ mol, preferably from 10 ⁻⁶ mol to 10 ⁻² mol, relative to 1 mol of the alkenyl group of the polymer (B). Is more preferable. If the content of the hydrosilylation catalyst (C) is less than 10 ⁻⁸ mol, curing may not proceed sufficiently. Moreover, when there is more content of a hydrosilylation catalyst (C) than 10 ^<-1> mol, the control of hardening of a liquid resin composition may be difficult, and the obtained modified silicone resin foam may be colored.

-About foaming agent (D) The foaming agent (D) in the present invention is preferably a chemical foaming agent that decomposes by heating to generate an inorganic gas such as carbon dioxide or nitrogen gas. Type foaming agents, inorganic pyrolytic foaming agents, inorganic reactive foaming agents, and the like.
Examples of the organic pyrolytic foaming agent include azo compounds, nitroso compounds, hydrazine derivatives, semicarbazide compounds, tetrazole compounds, and organic acids. Examples of the inorganic pyrolytic foaming agent include bicarbonate, carbonate, organic acid salt, and nitrite. Examples of the inorganic reactive foaming agent include a combination of bicarbonate and an organic acid or an organic acid salt.

  Examples of the azo compound include azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), barium azodicarboxylate, diazoaminobenzene, and the like. Examples of the nitroso compound include dinitrosopentamethylenetetramine (DPT).

  Examples of the hydrazine derivative include p, p'-oxybis (benzenesulfonylhydrazide) (OBSH), paratoluenesulfonyl hydrazide (TSH), hydrazodicarbonamide (HDCA), and the like.

  Examples of the semicarbazide compound include p-toluenesulfonyl semicarbazide. Examples of the tetrazole compound include 5-phenyltetrazole, 1-H tetrazole salt, 1,4-bistetrazole and the like.

  Examples of the organic acid include polyvalent carboxylic acids such as citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, and tartaric acid.

  Examples of the organic pyrolytic foaming agent further include trihydrazinotriazine. Examples of the bicarbonate include sodium bicarbonate and ammonium bicarbonate. Examples of the carbonate include sodium carbonate and ammonium carbonate.

  Examples of the organic acid salt include metal salts such as sodium, potassium, calcium, magnesium, ammonium, aluminum, and zinc of the organic acid. Examples of nitrites include ammonium nitrite.

  Of these, the foaming agent (D) of the present invention is preferably decomposed in a temperature range where the curing reaction (hydrosilylation reaction) of the curing agent (A) and the polymer (B) proceeds appropriately. A mixture of a salt and an organic acid is preferred. Examples of the bicarbonate include sodium bicarbonate and ammonium bicarbonate. Examples of the organic acid include citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, and tartaric acid. Further, a mixture of a bicarbonate and a metal salt of an organic acid can be preferably used as well.

  For example, in the case of a chemical foaming agent comprising a bicarbonate and an organic acid or an organic acid salt, the content of the foaming agent (D) is 1 with respect to 100 parts by weight of the polymer (B). The weight is preferably 20 parts by weight or more and more preferably 2 parts by weight or more and 15 parts by weight or less. The ratio of bicarbonate to organic acid or organic acid salt is preferably such that bicarbonate / organic acid or organic acid salt (weight ratio) is ¼ or more and 3 or less, and １ ／ or more and 2 or less. Is more preferable.

  If the content of bicarbonate is low or the ratio of bicarbonate to organic acid is low, the amount of carbon dioxide that is thermally decomposed is small, and the expansion ratio may decrease. Also, if the content of bicarbonate is high or the ratio of bicarbonate to organic acid is high, the amount of carbon dioxide gas that is thermally decomposed is large, the balance between foaming and curing is lost, and foaming cells are enlarged, resulting in poor foaming. May become a body.

  In the present invention, a foaming agent other than the above foaming agent (D) may be used in combination. For example, it is usually used for organic foams such as polyurethane, phenol, polystyrene, polyolefin, etc., and is a volatile liquid at room temperature and atmospheric pressure. And gaseous physical foaming agents. The physical foaming agent is not particularly limited as long as it does not inhibit the decomposition or hydrosilylation reaction of the chemical foaming agent. From the viewpoint of foamability, workability and safety, the boiling point of the physical foaming agent is 100 ° C. or less. Preferably, it is 65 ° C. or lower, particularly 50 ° C. or lower. Specific examples include organic compounds such as hydrocarbons, chlorofluorocarbons, alkyl chlorides and ethers, and inorganic compounds such as carbon dioxide, nitrogen and air. From the viewpoint of environmental compatibility, hydrocarbons, ethers, carbon dioxide and nitrogen. It is preferable to use a compound selected from air.

  Hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3- Examples thereof include dimethyl butane crobutane, cyclopentane, and cyclohexane. Examples of ethers include 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. Examples include ether.

  In addition, when performing mechanical stirring in the air at the time of foam manufacture, a bubble may be formed by the air entrained with stirring, and this is also contained in a physical foaming agent. However, when these physical foaming agents are used, there are concerns about changes in physical properties after foam molding due to residuals, etc., so that after foam production, by heating and curing at a temperature equal to or higher than the boiling point of the physical foaming agent used. It is preferable to remove the residual foaming agent.

・ Reactive lubricant (E)
The modified silicone resin foam of the present invention contains a reactive lubricant (E). By containing the reactive lubricant (E), it is possible to reduce friction and adhesion in the foamed cell of the modified silicone resin foam, and to obtain a foam having desired tactile sensation and flexibility.

  The lubricant (E) that can be used in the present invention is a reactive lubricant having a functional group equivalent of 500 g / mol to 8000 g / mol.

  The reactive lubricant (E) in the present invention contains a functional group having reactivity with the hydrosilyl group of the curing agent (A) or the alkenyl group of the polymer (B) in the molecule. ) And / or the polymer (B), the bleed-out of the reactive lubricant (E) to the outside of the foam system is suppressed, and the blending effect can be maintained over a long period of time.

  The functional group equivalent of the reactive functional group in the reactive lubricant (E) in the present invention is preferably 500 g / mol to 8000 g / mol, preferably 600 g / mol to 5000 g / mol, more preferably 700 g / mol. 4000 g / mol or less is more preferable. If the functional group equivalent is too small, the reactivity with the curing agent (A) or the polymer (B) increases, and the hydrosilylation reaction between the hydrosilyl group of the curing agent (A) and the alkenyl group of the polymer (B) is inhibited. However, the balance between foaming and curing cannot be achieved, resulting in a defective structure. If the functional group equivalent is too large, the reactive lubricant (E) tends to bleed out of the system and the blending effect tends to be difficult to obtain.

  The functional group equivalent is preferably 1000 g / mol or more and 3500 g / mol or less from the viewpoint of little change in hardness with time. Moreover, from the surface of a touch, 1000 g / mol or more and 2000 g / mol or less are preferable.

  As for the number average molecular weight of the reactive lubricant (E) in the present invention, the number average molecular weight Mn is preferably 500 or more and 30000 or less, more preferably 1000 or more and 20000 or less, from the viewpoints of processability and dispersibility. preferable.

  As the functional group of the reactive lubricant (E) in the present invention, vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexane Examples include hexenyl groups, alkenyl groups such as methacryl groups, hydrosilyl groups, silanol groups, epoxy groups, carbinol groups, mercapto groups, carboxyl groups, and the hydrosilyl group of the curing agent (A) or the alkenyl group of the polymer (B). From the viewpoint of reactivity, an alkenyl group, a hydrosilyl group, and a silanol group are preferable.

The reactive lubricant (E) in the present invention is preferably a liquid lubricant, more preferably an organopolysiloxane-based lubricant, and examples of the organopolysiloxane containing a reactive functional group include vinyl polydimethylsiloxane at both ends, Vinyl group-containing organopolysiloxanes such as terminal vinyldimethylsiloxane-diphenylsiloxane copolymer, both terminal vinylphenylmethylsiloxane, trimethylsilyl-blocked vinylmethylsiloxane-dimethylsiloxane copolymer, vinyl T-structure polymer, vinyl group-containing cyclic dimethylpolysiloxane,
Both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-capped dimethylpolysiloxane, both ends dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends Hydrosilyl group-containing organopolysiloxanes such as trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer at both ends,
Examples include silanol group-containing organopolysiloxanes such as hydroxy-terminated polydimethylsiloxane.

  In addition, these may use 1 type and may use 2 or more types by arbitrary ratios and combinations.

  The reactive lubricant (E) can be synthesized by a known method, and those commercially available can be used as they are. Examples of vinyl group-containing organopolysiloxane include DMS-V21 (manufactured by Gelest, functional group equivalent 3000 g / mol), DMS-V22 (manufactured by Gelest, functional group equivalent 4700 g / mol), DMS-V25 (manufactured by Gelest). , Functional group equivalent 8600 g / mol). As hydrosilyl group-containing organopolysiloxane, for example, HMS-082 (manufactured by Gelest, functional group equivalent 925 g / mol), HMS-071 (manufactured by Gelest, functional group equivalent 1100 g / mol), HMS-031 (manufactured by Gelest) , Functional group equivalent 1600 g / mol), DMS-H11 (manufactured by Gelest, functional group equivalent 550 g / mol), DMS-H21 (manufactured by Gelest, functional group equivalent 3000 g / mol) and the like. Examples of the silanol group-containing organopolysiloxane include DMS-S12 (manufactured by Gelest, functional group equivalent: 275 g / mol).

  The addition amount of the reactive lubricant (E) in the present invention is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and particularly preferably 5 parts by weight or more with respect to 100 parts by weight of the polymer (B). . Further, it is preferably 20 parts by weight or less, more preferably 18 parts by weight or less. If the amount of the reactive lubricant added is small, the friction and adhesion in the foam cell are not sufficiently suppressed, and it is difficult to obtain the desired tactile sensation and flexibility. If too much, the expansion ratio of the modified silicone resin foam decreases. Or bleed out of the reactive lubricant to the outside of the system.

  The modified silicone resin constituting the modified silicone foamable liquid resin composition of the present invention has a hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol, at least one alkenyl group in the molecular chain, Polymer (B) in which the repeating unit constituting the main chain is an oxyalkylene-based unit, hydrosilylation catalyst (C), blowing agent (D), and reactive lubrication having a functional group equivalent of 500 g / mol to 8000 g / mol A foamable liquid resin composition comprising the agent (E). From the viewpoint of touch and flexibility, the hydrosilyl group content in the foamable resin composition is preferably 0.5 mol to 10 mol per mol of alkenyl groups. It is preferably 7.5 mol or less, more preferably 0.5 mol or more and 5.0 mol or less, and particularly preferably 0.7 mol or more and 3.0 mol or less.

  When the hydrosilyl group content is low, the curing rate when the foamable liquid resin composition of the present invention is cured by the hydrosilylation reaction is slowed, and the balance between foaming and curing cannot be achieved, resulting in a defective structure. In addition, when the hydrosilyl group content increases, a large amount of hydrosilyl groups are likely to remain in the foam even after curing, and the curing reaction (crosslinking) proceeds due to the influence of temperature and the like even after forming the product form. Tend to. For this reason, it becomes a cause of deterioration of tactile sensation and flexibility over time and compression residual strain.

Other additives Addition to the modified silicone resin foam of the present invention includes a light-resistant stabilizer, an ultraviolet absorber, a storage stabilizer, a bubble regulator, a surfactant, a plasticizer, etc., unless the effects of the present invention are impaired. You may add as needed.

  Examples of the light-resistant stabilizer include hindered phenol antioxidants and hindered amine light stabilizers that do not contain sulfur atoms, phosphorus atoms, primary amines, and secondary amines. Here, the light-resistant stabilizer is a function that absorbs light having a wavelength in the ultraviolet region and suppresses the generation of radicals, or a function that captures radicals generated by light absorption and converts them into heat energy to render them harmless. And a compound that enhances stability to light.

  The ultraviolet absorber is not particularly limited, and examples thereof include benzoxazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. Here, the ultraviolet absorber is a compound having a function of absorbing light having a wavelength in the ultraviolet region and suppressing generation of radicals.

  The addition amount of the light-resistant stabilizer and the ultraviolet absorber in the present invention is preferably 0.01 parts by weight or more and 5 parts by weight or less, and 0.1 parts by weight or more with respect to 100 parts by weight of the polymer (B). 3 parts by weight or less is more preferable, and 0.3 part by weight or more and 2.0 parts by weight or less is more preferable. When the addition amount of the light-resistant stabilizer and the ultraviolet absorber is within this range, it is easy to obtain the effect of suppressing the increase in surface tack over time.

  As the storage stability improver, any conventional stabilizer known as a storage stabilizer for the curing agent (A) can be used as long as it achieves the intended purpose.

  Preferable examples of the storage stability improver include, for example, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide. These may be used alone or in combination of two or more. Specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole, vitamin E, 2- (4-morphodinyldithio) benzothiazole, 3-methyl-1-buten-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyn-3-ol 2-methyl-3-butyn-2-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene, and the like.

The amount of the storage stability improver used in the present invention can be selected almost arbitrarily as long as it is uniformly dispersed in the curing agent (A) and the polymer (B), but the SiH group in the curing agent (A) can be selected. It is preferably used in the range of 10 ⁻⁶ mol or more and 10 ⁻¹ mol or less with respect to ¹ mol. When the amount of the storage stability improver used is less than 10 ⁻⁶ mol, the storage stability of the curing agent (A) may not be sufficiently improved. When it exceeds 10 ⁻¹ mol, the curability becomes insufficient. There is.

  If necessary, a foam regulator may be added to the modified silicone resin foam of the present invention. There are no particular limitations on the type of cell regulator, and commonly used, for example, inorganic solid powders such as talc, calcium carbonate, magnesium oxide, titanium oxide, zinc oxide, carbon black, silica, silicone oil compounds, fluorine System compounds and the like. These may be used alone or in combination of two or more.

  In the present invention, the amount of use of the air conditioner is 0.1 parts by weight or more and 100 parts by weight or less when the total amount of the curing agent (A), polymer (B), and hydrosilylation catalyst (C) is 100 parts by weight. Is preferable, and 0.5 to 50 parts by weight is more preferable.

  In the present invention, the compatibility of the foamable liquid resin composition comprising the curing agent (A), the polymer (B), the hydrosilylation catalyst (C), the foaming agent (D), and the reactive lubricant (E) is improved. For this purpose, a surfactant may be added.

  Specific examples of surfactants include alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkyl ether acetate, lauryl trimethyl ammonium chloride, alkoxy chloride Propyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride solution, alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropyl betaine, glycerin fatty acid ester, propylene glycol fatty acid ester, Nonionic surfactants, such as sorbitan fatty acid ester, etc. are mentioned. These may be used alone or in combination of two or more.

  In the present invention, a silicone surfactant such as a polyoxyalkylene-polydimethylsiloxane block copolymer is added for the purpose of improving the compatibility of the curing agent (A) and the reactive lubricant (E). You can also.

  The polyoxyalkylene-polydimethylsiloxane block copolymer is not particularly limited. For example, in addition to an AB type diblock body, an ABA type triblock body, an (AB) n type multiblock body, a branched type, A pendant type, a star type, etc. are mentioned. In addition, specific structures of polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the terminal structure is also OH. Examples thereof include a base end, an ether end such as methoxy and t-butoxy, and a reactive allyl group end.

In the present invention, a plasticizer can be added for the purpose of adjusting the flexibility and moldability of the modified silicone resin foam.
The plasticizer in the present invention is a compound in which the repeating unit constituting the main chain is composed of an oxyalkylene unit and the number average molecular weight is less than 15,000.

  In the plasticizer of the present invention, the repeating unit constituting the main chain is composed of an oxyalkylene unit. Specific examples of the main chain include polyethylene oxide, polypropylene oxide, polybutylene oxide; two or more random or block copolymers selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. These may be used alone or in combination of two or more. Of these, polypropylene oxide is preferable from the viewpoint of compatibility with the polymer (B).

  The molecular weight of the plasticizer in the present invention is 1000 or more as the number average molecular weight and preferably 3000 or more from the viewpoint of flexibility of the resulting modified silicone resin foam and prevention of outflow of the plasticizer to the outside of the system. If the number average molecular weight of the plasticizer is lower than 1000, the plasticizer will flow out of the system over time due to heat, compression, etc., and the initial physical properties cannot be maintained over a long period of time, and there is a concern about adverse effects on the tactile sensation. . Further, if the number average molecular weight of the plasticizer becomes too high, the plasticizing effect cannot be obtained, and the viscosity becomes high and the workability deteriorates, so that it is preferably less than 15000, more preferably less than 10,000.

  The plasticizer in this invention may have a reactive functional group in the range which does not inhibit the hardening reaction of a hardening | curing agent (A) and a polymer (B). Examples of the reactive functional group of the plasticizer include vinyl group, allyl group, methyl vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, methacryl group, etc. Alkenyl group, hydroxyl group, amino group, carboxyl group, isocyanate group and the like.

  In addition, if the plasticizer of this invention can provide a softness | flexibility to a modified silicone resin foam, there will be no limitation in particular even if it is linear or branched.

  The addition amount of the plasticizer in the present invention is preferably 5 parts by weight or more and 150 parts by weight or less, more preferably 10 parts by weight or more and 120 parts by weight or less, and more preferably 20 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the polymer (B). More preferred are parts by weight or less. When the addition amount of the plasticizer is less than 5 parts by weight, the effect of imparting flexibility may be insufficient. When it exceeds 150 parts by weight, the mechanical strength of the modified silicone resin foam is insufficient or the expansion ratio is reduced. Tend.

  The manufacturing method of a plasticizer is not specifically limited, A well-known manufacturing method can be applied, and also a commercially available compound may be used.

  In the present invention, as necessary, a filler, a radical inhibitor, an adhesion improver, a flame retardant, a foam stabilizer, an acid or basic compound, a storage stability improver, an ozone deterioration inhibitor, a thickener. , Coupling agents, conductivity imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, pigments, metal deactivators, physical property modifiers, and the like. It can be added as long as it is not impaired.

-About the manufacturing method of a modified silicone resin foam The manufacturing method of a modified silicone resin foam is a hardening | curing agent (A), a polymer (B), a hydrosilylation catalyst (C), a foaming agent (D), a reactive lubricant ( If the foamable liquid resin composition comprising E) is cured and foamed, it can be produced without any particular limitation.

  As a method for producing the foamable liquid resin composition, the components of the curing agent (A), the polymer (B), the hydrosilylation catalyst (C), the foaming agent (D), and the reactive lubricant (E) are mixed. Although there is no limitation in particular, it is preferable that each component in the foamable liquid resin composition is well mixed. The mixing order of each component is not particularly limited, but after the polymer (B), the hydrosilylation catalyst (C) and the foaming agent (D) are mixed in advance, the curing agent (A) and the reactive lubricant (E) are added. It is preferable to produce a foamable liquid resin composition by mixing.

  The foamable liquid resin composition can be mixed and then poured into a mold or spread on a substrate on a belt conveyor, and then foamed to obtain a foam. In the foamable liquid resin composition of the present invention, a hydrosilylation reaction by a hydrosilyl group and an alkenyl group occurs, and the curing agent (A) and the polymer (B) form (cured) a network (crosslinked) structure. Curing (hydrosilylation reaction) may be performed at any time as long as curing is not completed before foaming, but it is preferable to foam before curing or foam simultaneously with curing.

  At the time of curing and foaming, it is preferable that the foaming agent (D) to be used decomposes in a temperature region where the curing reaction (hydrylylation) of the curing agent (A) and the polymer (B) proceeds appropriately. Is preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 140 ° C. or lower, and particularly preferably 55 ° C. or higher and 130 ° C. or lower. Within this temperature range, curing and foaming of the foamable liquid resin composition proceed in a well-balanced manner, and a preferred modified silicone resin foam of the present invention is obtained.

  The time (heating time) for holding at the above temperature is not particularly limited, but it is preferable to hold at a temperature of 5 minutes to 3 hours, further 10 minutes to 2 hours, particularly 20 minutes to 90 minutes. The modified silicone resin foam of the invention is obtained.

  Furthermore, since the obtained modified silicone resin foam tends to be able to reduce compressive residual strain, it is preferable to perform heat curing. The conditions for the heat curing are not particularly limited, but it is preferable to perform the heat curing at 40 ° C. or more and 200 ° C. or less for 10 minutes or more and 72 hours or less because the compression residual strain is reduced.

  The compression residual strain of the modified silicone resin foam of the present invention is preferably 10% or less, and more preferably 8% or less. When the compressive residual strain is small, for example, when used as a cushion, the strain at the time of use is small, and it is possible to exhibit excellent restoring properties. In addition, the compression residual distortion in this invention is implemented according to JISK6400-4, after compressing a foam 75% on 40 degreeC and 8-hour conditions, after that it opened at room temperature, and was made to recover | recover for 30 minutes The rate of decrease in thickness relative to the original thickness.

The modified silicone resin foam of the present invention preferably has a density of 300 kg / m ³ or less, more preferably 270 kg / m ³ or less, more preferably 250 kg / m ³ or less, and particularly preferably 230 kg / m ³ or less. . When the density is within this range, for example, when it is commercialized as a cushion, it is preferable because it is relatively light and can be easily carried on a daily basis.

The lower limit of the density of the foam is not particularly limited, but if a strong and preferable value is exemplified, it is preferably 25 kg / m ³ or more, more preferably 30 kg / m ³ or more, and further 50 kg / m ^3. In particular, kg / m ³ or more is preferable. When the density is too small, for example, when used as a cushion, it may bottom out due to compression.

  The modified silicone resin soft foam of the present invention preferably has a hardness with a hardness meter for tofu at 25 ° C. (manufactured by Oba Keiki Seisakusho Co., Ltd.) of 0.80 N or less, more preferably 0.70 or less. Further, it is preferably 0.60 or less, particularly preferably 0.50 or less. If it is the said range, it can be said that it is a flexible property.

  The form of the modified silicone resin foam of the present invention is not particularly limited, and examples thereof include a plate shape, a sheet shape, an indeterminate lump shape, a bead shape, or a bag shape or a shape formed in a clothing. . The foam may be used alone, or may be used integrally with other types of foams such as urethane foams, gels, plastics, rubbers, films, textiles such as cloth and non-woven fabric, and materials such as paper.

  Furthermore, a cloth or a nonwoven fabric made of cotton, acrylic fiber, hair, polyester fiber or the like may be appropriately bonded to the surface of the modified silicone resin foam of the present invention using an adhesive. By sticking together in this way, the tactile feel of the foam can be further improved, and depending on the application, a sweat-absorbing action can be applied by the bonded fabric during sweating at the time of exercise or high temperature / humidity.

  The shape of the modified silicone resin foam of the present invention is not particularly limited, but a polygon such as a rectangle, square, circle, ellipse or rhombus, or a rectangular or doughnut-shaped interior is hollowed out. And those with arbitrary irregularities on the surface. Moreover, you may make a through-hole suitably in order to give air permeability.

  The modified silicone resin foam of the present invention has high flexibility and good tactile sensation, and has a small compressive residual strain. Therefore, the modified silicone resin foam can be used for various applications that can effectively exhibit such physical properties. In addition, since isocyanate is not used, it can be suitably used for applications such as transportation equipment, bedding, furniture, various equipment, building materials, packaging materials, medical materials, etc., as a soundproofing material, vibration damping material, cushioning material, etc. .

  Examples of applications that can effectively demonstrate the excellent tactile sensation and flexibility of the modified silicone resin foam of the present invention include, for example, transportation equipment applications such as seats for automobiles, construction machinery, railway vehicles, ships, and aircraft, child seats, headrests, armrests. , Footrests, headliners, saddles / rider cushions for motorcycles / bicycles, custom car bed mats, camper cushions, etc., skin materials / skin lining materials, ceiling materials, handles, door trims, instrument panels, dashes Boards, door panels, pillars, console boxes, quarter trims, sun visors, flexible containers, front mirrors, harnesses, dust covers and other core materials and skin / skin lining materials, floor cushions and other damping and sound absorbing materials, helmet linings, Rush pad, a cushioning material such as center Pila garnish, energy absorbing bumpers, guard acoustic insulation, vehicle wax sponge, and the like.

  As bedding / bedding products, cushion materials such as pillows, comforters, mattresses, beds, mattresses, bed mats, bed pads, cushions, cribs, baby neck pillows, and skin / skin lining materials may be used.

  Furniture applications include cushions such as chairs, seat chairs, cushions, sofas, sofa cushions / seat cushions, carpets / mats, tatami mats / comforters, toilet mats, and skin / skin lining materials. It is done.

  Examples of various equipment applications include seals and cushioning materials for liquid crystals and electronic parts, robot skin, conductive cushion materials, antistatic cushion materials, pressure sensing materials, and the like.

  Various cleaning sponge applications include cleaning cleaners, dishwashing cleaners, body cleaning cleaners, shoe polish cleaners, car wash cleaners, and the like.

  Examples of toiletries include absorbent materials such as diapers and sanitary napkins, side gathers and various liquid filters.

Examples of footwear applications include shoe skin materials, linings, insoles, shoe rub prevention pads, various shoe pads, inner boots, slippers, slipper cores, sandals, sandal insoles, and the like.
Examples of cosmetic tools include cosmetic puffs and eye color chips.

  Various miscellaneous goods are used for bath products such as bath pillows, massage puffs, mouse pads, keyboard armrests, anti-slip cushions, stationery (pen grips, penetrating seals), desk pillows, earplugs, cotton swabs, hot pack seats , Cold pack seats, compresses, glasses pads, underwater spectacles pads, face protectors, watch pads, headphone ear pads, earphones, ice pillow covers, folding pillows and other core materials, cushion materials, skin materials / skin lining materials, both sides Adsorption media, such as a tape base material, a fragrance | flavor, a stamp stand, etc. are mentioned.

Apparel applications include pad materials such as shoulders and bras, liners such as cold protection materials, and heat insulating materials.

  Sports applications include sports protectors, bouldering (climbing and rock climbing climbing rocks of 2 to 3 m) mat, beat boards, high jump cushion materials, landing mats for gymnastics and exercise, kids mats, etc. Examples thereof include liners for materials, skin materials, skin lining materials, ski boots, snowboard boots, and the like.

  For toys and playground equipment, hand exercisers, healing goods, key holders, stuffed animals, mannequin bodies, balls, cushioning materials such as massage balls, padding materials, skin materials, skin lining materials, special shapes such as ornaments and monsters, various types Examples include casting materials for article shape molding and model production, article shape molding materials in casting methods, model sample preparation materials from molds, decorative article preparation materials, monster special moldings and moldings, etc. .

As medical / nursing care, cell sheets for regenerative medicine, artificial skin, artificial bone, artificial cartilage,
Artificial organs, other biocompatible materials, chemical exudation pads, hemostatic pads, gas-liquid separation filters (indwelling needle filters), adhesives, medical liquid absorption tools, masks, compression pads, surgical disposable products, low frequency treatment devices Electrode pads, bedsore prevention mattresses, posture change cushions, wheelchair cushions, wheelchair seats, shower chairs and other nursing care products, bathing care pillows, contractor palm protectors, taping, cast liners, prosthetic and prosthetic liners, Cases, tooth bases, etc. Can be used for dental supplies, shock absorbing pads, hip protectors, elbow / knee protectors, wound dressings, etc.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

  The measurement and evaluation in the examples and comparative examples were performed under the following conditions and methods. Unless otherwise specified, “parts” and “%” in Examples and Comparative Examples indicate “parts by weight” and “% by weight”.

<Foam density>
A cube of about 30 mm square was cut out from the obtained modified silicone resin foam, the volume was calculated by measuring the size of three sides, and the density was calculated by removing it from the measured weight.

<Tactile sense>
The tactile sensation when the obtained modified silicone resin foam was compressed with a palm was evaluated according to the following criteria, and passed with a Δ or higher.
A: It is soft and comfortable to touch. Further, when it is pushed to the bottom with a finger and shifted to the side, it can be laterally deformed with a slight force, and the amount of deformation is large. (Same as gel material.)
○: When the finger is pushed down until it feels bottoming and is shifted to the side, it can be deformed with low force.
○ △: When the finger is pushed down until it feels bottoming and is shifted to the side, it can be deformed with a moderate force.
Δ: Pushing with a finger until a feeling of bottoming is felt, and when it is shifted to the side, if it is a strong force, it can be laterally deformed.
Δ ×: Pushing with a finger until a feeling of bottoming is felt, and when it is shifted to the side, if it is a strong force, it can be laterally deformed, but the deformation is small.
×: Pushing with a finger until a feeling of bottoming is felt, and when it is shifted to the side, it cannot be laterally deformed even with a strong force.

<Flexibility>
The obtained modified silicone resin foam was cut into cubes of about 30 mm square and evaluated with a tofu hardness meter [manufactured by Oba Keiki Seisakusho].

<Compressive residual strain>
According to JIS K 6400-4 C method, it implemented by 40 degreeC, 8 hours, and 75% compression.

<Raw materials>
In the examples and comparative examples, the raw materials shown in Table 1 were used.

(Synthesis of curing agent (A-1))
(-Si-O-) 0.5-equivalent α-methylstyrene of the total amount of hydrosilyl groups in the presence of a platinum catalyst is added to a trimethylsiloxy group-blocked methylhydrogenpolysiloxane having 10 repeating units on average. A compound having an average of 5 hydrosilyl groups in one molecule (a curing agent (A-1) was obtained. The number average molecular weight Mn of this compound was 1190, and the functional group equivalent of the hydrosilyl group was 238 g / mol (compound Was added to 30% ethanolic potassium hydroxide, and the amount of hydrogen generated was measured with a WS-type wet gas meter to estimate the functional group equivalent of the hydrosilyl group in the compound.

(Synthesis of polymer (B-1))
An oxypropylene polymer glycol having a number average molecular weight of 3000 was obtained by a polymerization method using caustic alkali. Propylene oxide was polymerized using the obtained oxypropylene polymer glycol as an initiator and a composite metal cyanide complex catalyst (zinc hexacyanocobaltate) to obtain a polymer having a number average molecular weight of 28,000. The polymer is converted to an allyl group using a 28% methanol solution of sodium methylate and allyl chloride, and then desalted and purified to have approximately two allyl group ends in one molecule. A polyoxyalkylene polymer (polymer (B-1)) was obtained. The functional group equivalent of the allyl group of the obtained polymer was 8333 g / mol (the amount of allyl group was measured by titration by a method based on JIS K1557).

(Examples 1-8), (Comparative Examples 1-8)
In 100 parts of the polymer (B) in a 1 L disposable cup, 1.0 part each of the light-resistant stabilizer-1, the light-resistant stabilizer-2, and the UV absorber, and 5. each of the foaming agent (D). 0 parts (weight ratio: baking soda / citric acid = 1) were added and mixed well, and then kneaded with three paint rolls (manufactured by Kodaira Seisakusho) to prepare a master batch. To this master batch, 0.02 part of storage stability improver and 0.02 part of catalyst (C) were added and mixed well. Thereafter, reactive lubricants (E) and curing agents (A) listed in Tables 2 to 4 were mixed to obtain a foamable liquid resin composition.

  300 g of the obtained composition was poured into a mold (length 20 cm × width 20 cm × height 5 cm) and cured by heating in an oven set at 100 ° C. for 60 minutes to obtain a modified silicone resin soft foam. The obtained modified silicone resin was removed from the mold and cured by heating in an oven set at 120 ° C. for 120 minutes, and then the density, tactile sensation, flexibility, and compression residual strain of the modified silicone resin foam were evaluated. In addition, as a long-term evaluation, the modified silicone resin foam was heat-cured for 1 week in an oven set at 100 ° C. to evaluate tactile sensation and flexibility. The evaluation results are shown in Tables 2-4.

  From Tables 2-4, the foam obtained from the foamable liquid resin composition which mix | blended the reactive lubricant (E) of functional group equivalent 500g / mol or more and 8000g / mol or less becomes favorable in tactile sense, and a softness | flexibility. It can be seen that a good foam is obtained. Further, since the hydrosilyl group content in the foamable liquid resin composition is 0.5 mol or more and 10 mol or less per mol of alkenyl groups, the compressive residual strain is small, and the tactile sensation and flexibility due to changes with time are greatly changed. There is no problem for long-term use.

Claims (10)

A hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol,
A polymer (B) having at least one alkenyl group in the molecular chain, wherein the repeating unit constituting the main chain is an oxyalkylene-based unit;
Hydrosilylation catalyst (C),
Foaming agent (D) and
A foamable liquid resin composition comprising a reactive lubricant (E) having a functional group equivalent of 500 g / mol to 8000 g / mol,
A foamable liquid resin composition having a hydrosilyl group content in the foamable resin composition of 0.5 to 10 moles per mole of alkenyl groups. The foamable liquid resin composition according to claim 1, wherein the reactive lubricant (E) is an organohydrogenpolysiloxane. The foamable liquid resin composition according to claim 1 or 2, wherein the polymer (B) has a number average molecular weight of 15000 or more and 50000 or less. The foamable liquid resin composition according to any one of claims 1 to 3, wherein the repeating unit constituting the main chain of the polymer (B) is oxypropylene. The foamable liquid resin composition according to any one of claims 1 to 4, wherein the foaming agent (D) is a chemical foaming agent that decomposes by heating to generate an inorganic gas such as carbon dioxide gas or nitrogen gas. A hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol,
A polymer (B) having at least one alkenyl group in the molecular chain, wherein the repeating unit constituting the main chain is an oxyalkylene-based unit;
Hydrosilylation catalyst (C),
Foaming agent (D) and
Lubricant (E)
The foam formed by foaming the foamable liquid resin composition as described in any one of Claims 1-5. The modified silicone foam according to claim 6, which has a density of 30 kg / m ³ or more and 300 kg / m ³ or less. The foamable liquid resin composition according to claim 6 or 7, which has a compressive residual strain of 10% or less when compressed by 75% under conditions of 40 ° C and 8 hours. Hydrosilyl group-containing curing agent (A) having a functional group equivalent of less than 500 g / mol, a polymer having at least one alkenyl group in the molecular chain and a repeating unit constituting the main chain consisting of an oxyalkylene unit (B ), A hydrosilylation catalyst (C), a foaming agent (D), and a reactive lubricant (E), the foamable liquid resin composition is foamed. The manufacturing method of the foam of description. The method for producing a foam according to claim 9, wherein the foamable liquid resin composition is cured and foamed at a temperature of 40 ° C. or higher and 150 ° C. or lower.