JP5823878B2 - Foamable liquid resin composition and foam - Google Patents

Description

  The present invention relates to a foamable liquid resin composition, a foam, and a method for producing the same.

  A foam using a modified silicone resin has been proposed as a soft foam having good tactile sensation and excellent flexibility (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, has excellent flexibility such as low hardness and low rebound resilience, and is toxic. Isocyanate that is concerned is not used, and it is suitable as a material such as a soundproofing material, a vibration damping material, and a cushioning material.

  However, further improvements are desired for the tactile sensation and flexibility that change with time and the tendency for compressive residual strain to increase. Here, the compression residual strain is a phenomenon generally called sag.

  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 high, and the hardness of the foam is high, and it is difficult to say that the touch is excellent.

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

  An object of the present invention is to provide a foam having excellent tactile sensation and flexibility, in which changes in physical properties and compressive residual strain over time are suppressed.

  The present invention has the following configuration.

  1). A curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol to less than 180 g / mol, a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol to 700 g / mol, and having at least one alkenyl group. In addition, the polymer (B), the hydrosilylation catalyst (C), the foaming agent (D), the lubricant (E), and the repeating unit constituting the main chain consisting of an oxyalkylene unit, on average in the molecular chain A foamable liquid resin composition comprising a plasticizer (F) having an alkenyl group of less than 1 and a repeating unit constituting the main chain comprising an oxyalkylene-based unit, and containing the hydrosilyl group in the foamable liquid resin composition A foamable liquid resin composition having an amount of 1.1 to 5.0 moles per mole of alkenyl groups.

  2). The foamable liquid resin composition according to 1), wherein the polymer (B) has a number average molecular weight of 10,000 to 100,000.

  3). The foamable liquid resin composition according to 1) or 2), wherein the repeating unit constituting the main chain of the polymer (B) is oxypropylene.

  4). The foamable liquid resin composition according to any one of 1) to 3), wherein the foaming agent (D) is a chemical foaming agent that decomposes by heating to generate an inorganic gas.

5). The foamable liquid resin composition according to any one of 1) to 4), wherein the lubricant (E) is a silicone-based lubricant having a kinematic viscosity (25 ° C.) of 30 mm ² / s to 10,000 mm ² / s.

  6). The foamable liquid resin composition according to any one of 1) to 5), wherein the plasticizer (F) has a number average molecular weight of 1,000 to 30,000.

  7). The foamable liquid resin composition according to any one of 1) to 6), wherein the repeating unit constituting the main chain of the plasticizer (F) is oxypropylene.

  8). A curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol, a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less, and at least one in the molecular chain Polymer (B) having an alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene unit, hydrosilylation catalyst (C), blowing agent (D), lubricant (E), average in the molecular chain The foamable liquid resin composition according to any one of 1) to 7), wherein the repeating unit comprising less than one alkenyl group and the repeating unit constituting the main chain is composed of a plasticizer (F) comprising an oxyalkylene unit. A foam made by foaming a product.

9). The foam according to 8), wherein the density is 20 kg / m ³ or more and 350 kg / m ³ or less.

  10). The foam according to 8) or 9), wherein the compression residual strain is 10% or less when compressed by 75% under the condition of 40 ° C. for 8 hours.

  11). A curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol, a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less, and at least one in the molecular chain Polymer (B) having an alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene unit, hydrosilylation catalyst (C), blowing agent (D), lubricant (E), average in the molecular chain And foaming a foamable liquid resin composition comprising a plasticizer (F) having less than one alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene-based unit 8) to 10) The manufacturing method of the foam as described in any one.

  12). 11. The method for producing a foam according to 11), wherein the foamable liquid resin composition is cured and foamed at a temperature of 40 ° C. to 150 ° C.

  The foam obtained from the foamable liquid resin composition of the present invention is less likely to undergo a curing reaction (crosslinking) after the foam is produced, and can suppress deterioration in tactile sensation and flexibility over time and compression residual strain. 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.

  In the present invention, the curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol, the curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less, at least one Polymer (B) having an alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene unit, hydrosilylation catalyst (C), blowing agent (D), lubricant (E), average in the molecular chain A plasticizer (F) having less than one alkenyl group, the repeating unit constituting the main chain comprising an oxyalkylene unit, and having a hydrosilyl group content of 1.1 mol or more per mol of alkenyl groups A foamable liquid resin composition of less than or equal to 0 mol, a foam formed by foaming the composition, and a method for producing the foam.

-About hardening | curing agent (A) The hydrosilyl group equivalent in this invention is 30g / mol or more and less than 180g / mol hardening | curing agent (A-1), and the hydrosilyl group equivalent is 180g / mol or more and 700g / mol or less hardening | curing agent (A-). Since 2) has a hydrosilyl group, it has at least one alkenyl group and reacts with the alkenyl group present in the polymer (B) in which the repeating unit constituting the main chain is composed of an oxyalkylene unit (hydrosilylation). Reaction) and cure.

  By using two kinds of curing agents having different hydrosilyl group equivalents together, the three-dimensional network structure formed by the hydrosilylation reaction with the polymer (B) becomes strong, and a lubricant that adjusts tactile sensation and flexibility ( E) Bleed-out considered to be derived is suppressed, and the blending effect is maintained over a long period of time. In addition, the hydrosilyl group equivalent in this invention means what remove | divided the weight of 1 mol of molecules by the number of moles of the hydrosilyl group in 1 mol of molecules.

  The hydrosilyl group equivalent of the curing agent (A-1) needs to be 30 g / mol or more and less than 180 g / mol, but is 40 g / mol or more and 160 g / mol or less, more preferably 50 g / mol or more and 150 g / mol or less. preferable. In particular, 50 g / mol or more and 100 g / mol or less is preferable from the viewpoint of a low rate of change in hardness.

  Further, the hydrosilyl group equivalent of the curing agent (A-2) needs to be 180 g / mol or more and 700 g / mol or less, but 200 g / mol or more and 600 g / mol or less, and further 220 g / mol or more and 500 g / mol or less. Is preferred. By using the curing agent (A-1) and the curing agent (A-2) within the above range, not only a foam having a desired density is obtained, but also formed by a hydrosilylation reaction with the polymer (B). The resulting three-dimensional network structure is strengthened, bleed-out considered to be derived from the lubricant (E) that adjusts tactile sensation and flexibility, and the properties of the foam obtained over a long period of time can be maintained.

  When the amount of hydrosilyl groups in the curing agent (A-1) and the curing agent (A-2) is less than these ranges, the stability of the curing agent, that is, the stability of the foamable liquid resin composition is deteriorated or cured. It becomes difficult to obtain a low density foam. On the other hand, when the hydrosilyl group equivalent is larger than these ranges, the curing speed at the time of curing becomes slow, it becomes difficult to balance foaming and curing, and a foam that is good in terms of tactile sensation, flexibility, and additive bleed out is obtained. It becomes difficult to obtain. In addition, it becomes difficult to maintain the tactile sensation and flexibility over time.

  By using each of the curing agent (A-1) and the curing agent (A-2) alone, it is possible to obtain a foam having a desired tactile sensation and flexibility, but the curing agent (A-1 ) When used alone, the tactile sensation and flexibility tend to decrease with time, and when the curing agent (A-2) is used alone, the bleedout that is considered to be derived from the lubricant (E) tends to be remarkable.

  The curing agent (A) in the present invention is not particularly limited as long as the hydrosilyl group is in the main chain or side chain of the molecule as long as it is a compound containing a hydrosilyl group, and the molecular chain is not particularly limited. However, organohydrogenpolysiloxane is preferred from the viewpoint of availability of raw materials and 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 organohydrogenpolysiloxane having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol include, for example, KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd., hydrosilyl group equivalent 60 g / mol), KF-9901 ( Manufactured by Shin-Etsu Chemical Co., Ltd., hydrosilyl group equivalent 140 g / mol), HMS-991 (manufactured by Gelest, hydrosilyl group equivalent 67 g / mol), SH1107 (manufactured by Toray Dow Corning Co., Ltd.), TSF484 (Momentive Performance Materials) Product), H-Siloxane (Asahi Kasei Wacker Silicone Co., Ltd.), and the like.

  Examples of commercially available organohydrogenpolysiloxane having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less include, for example, HMS-301 (manufactured by Gelest, hydrosilyl group equivalent 245 g / mol), HMS-151 (Gelest). Manufactured, hydrosilyl group equivalent 490 g / mol).

  Moreover, in order to ensure compatibility with the polymer (B) and to adjust the amount of hydrosilyl groups, it is also possible to use those obtained by modifying the organohydrogenpolysiloxane with a compound having a carbon-carbon double bond. . Examples of the compound having a carbon-carbon double bond that can be used include a vinyl group-containing compound.

  Examples of the vinyl group-containing compound include α-olefins, aromatic group-containing compounds, and allyl group-containing compounds. Specific examples of the α-olefin include propylene, 1-butene, and 1-octene. Specific examples of the aromatic group-containing compound include styrene and α-methylstyrene. Specific examples of the allyl group-containing compound include allyl alkyl ether, allyl alkyl ester, allyl phenyl ether, and allyl phenyl ester.

  Among them, it is preferable to modify with an aromatic group-containing compound from the viewpoint of compatibility in the composition.

  In the case of modification using a compound having a carbon-carbon double bond, the amount of the compound having a carbon-carbon double bond used is 0.10 to 0.80 mole per mole of hydrosilyl group in the organohydrogenpolysiloxane. Further, it is preferably used so as to be 0.4 to 0.6 mol of carbon-carbon double bond.

  The compound having a carbon-carbon double bond used for modification may be used alone or in combination of two or more. In addition, modification with a compound having a carbon-carbon double bond can be applied to both the curing agent (A-1) and the curing agent (A-2). This is preferable because compatibility with the combined body (B) is ensured and handling becomes easy, and a decrease in tactile sensation due to aging can be prevented.

  The hydrosilyl group content in the foamable liquid resin composition of the present invention is determined from the reaction rate (curing rate) in the hydrosilylation reaction with the polymer (B) and the feel and flexibility of the foam. Although it is necessary to mix | blend so that it may become 1.1 mol or more and 5.0 mol or less per mol, it becomes 1.2 mol or more and 4.5 mol or less, Furthermore, it becomes 1.2 mol or more and 4.0 mol or less. It is preferable to blend as described above. Moreover, it is preferable to mix | blend so that it may become 1.2 mol or more and 3.0 mol or less from the point with the small rate of change of the hardness after a time-dependent change.

  The curing agent (A-1) is preferably used so that the hydrosilyl group content of the curing agent (A-1) is 0.2 mol or more and 4.0 mol or less per mol of the alkenyl group. It is preferably used in the range of 3.5 mol or less, particularly 0.2 mol or more and 3.0 mol or less.

  The curing agent (A-2) is preferably used so that the hydrosilyl group content of the curing agent (A-2) is 0.8 mol or more and 1.2 mol or less per mol of the alkenyl group. It is preferably used in the range of 85 to 1.15 mol, particularly 0.9 to 1.1 mol.

  When the hydrosilyl group content is low, the three-dimensional network structure formed by the hydrosilylation reaction with the polymer (B) does not become strong, and the bleedout considered to be derived from the lubricant (E) tends to be remarkable. It is in. Further, when the hydrosilyl group content is increased, a large amount of hydrosilyl groups are likely to remain after the foam is produced, and the tactile sensation and flexibility tend to decrease with time.

The kinematic viscosity at 25 ° C. of the lubricant (E) is ^{2 to} 15 parts by weight per 100 parts by weight of the polymer (B) at 75 mm ² / s to 5000 mm ² / s, and the curing agent (A-1) and curing are performed. The blending ratio of the agent (A-2) (total number of moles of hydrosilyl groups in the curing agent (A-1) / total number of moles of hydrosilyl groups in the curing agent (A-2)) is 0.7 to 2.5, Furthermore, by using it so that it may become 0.75-2.0, it is preferable at the surface from which the bleed-out of the foam obtained decreases.

Further, the kinematic viscosity at 25 ° C. of the lubricant (E) is preferably 30, more preferably 40 mm ² / s to 2000, and further 1000 mm ² / s to 5 to 25 weight per 100 parts by weight of the polymer (B). Parts, and further, 10 to 20 parts by weight, and the mixing ratio of the curing agent (A-1) and the curing agent (A-2) (total number of hydrosilyl groups in the curing agent (A-1) / curing agent (A- 2) The total number of moles of hydrosilyl groups) is 0.7 to 2.5, more preferably 0.75 to 2.0. Less preferred.

-About a polymer (B) The polymer (B) in this invention is a polymer which has at least 1 alkenyl group and the repeating unit which comprises a principal chain consists of an oxyalkylene type unit. An alkenyl group is a group containing a carbon-carbon double bond that is active for hydrosilylation reactions. The alkenyl group is preferably an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, more preferably 2 to 4 carbon atoms (eg, vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group). Group, hexenyl group, etc.), preferably a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 6 carbon atoms (eg, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc.) ), A methacryl group and the like.

  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, the hydrosilylation reaction occurs to be a polymer and is cured. 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, both of the main chains are required. It is preferable that an alkenyl group is present at the terminal or the terminal of the molecular chain at the branched portion.

  There are no particular limitations on the manner of bonding of the alkenyl group to the polyoxyalkylene polymer, such as a direct bond of the alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, a urea bond, or an alkyl group that does not participate in the hydrosilylation reaction. Examples include binding through a spacer component.

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. Can do. 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.).

  The molecular weight of the polymer (B) in the present invention is preferably a number average molecular weight Mn of 10,000 or more, more preferably 15000 or more, particularly 17000, from the viewpoint of the balance between flexibility, touch and reactivity. The above is preferable. The upper limit of the number average molecular weight Mn is not particularly limited, but is preferably 100,000 or less, more preferably 60000 or less, and further preferably 40000 or less.

-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 10 ^-8 mol or more and 10 ^-1 mol or less, preferably 10 ^-6 mol or more and 10 ^-2 mol or less, with respect 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. On the other hand, when the content of the hydrosilylation catalyst (C) is more than 10 ⁻¹ mol, it may be difficult to control the curing of the liquid resin composition or the obtained foam may be colored.

-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 gas or nitrogen gas. An azo compound, a nitroso compound, a hydrazine derivative, a semicarbazide Organic thermal decomposition foaming agents such as compounds, tetrazole compounds, organic acids, etc., inorganic thermal decomposition foaming agents such as bicarbonates, carbonates, organic acid salts, nitrites, bicarbonates and organic acids or organics Examples thereof include inorganic reactive foaming agents such as acid salt combinations.

  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.

  For example, in the case of a chemical foaming agent composed of bicarbonate and an organic acid, the content of the foaming agent (D) is 1 to 20 parts by weight with respect to 100 parts by weight of the polymer (B). The amount is preferably less than parts by weight, more preferably 2 parts by weight or more and less than 15 parts by weight. As for the ratio of bicarbonate to organic acid, bicarbonate / organic acid (weight ratio) is preferably 1/4 or more and less than 5, and more preferably 1/3 or more and less than 3. 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 be reduced. If the content of bicarbonate is high If the amount of foaming is large and the amount of soot is increased, and the ratio of bicarbonate and organic acid is high, the amount of reaction with the organic acid decreases, the amount of carbon dioxide gas decreases, and the expansion ratio may decrease.

Under normal temperature and atmospheric pressure, a volatile liquid or gaseous physical foaming agent can be used in combination with a chemical foaming agent.
The physical foaming agent is not particularly limited as long as it does not inhibit the decomposition of the chemical foaming agent or the hydrosilylation reaction. For example, a foaming agent used for foaming polyurethane, phenol, polystyrene, polyolefin and the like can be used. . As the physical foaming agent, the boiling point of the physical foaming agent is preferably 100 ° C. or less, more preferably 65 ° C. or less, and particularly preferably 50 ° C. or less from the viewpoint of foamability, workability and safety. 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.

-Lubricant (E) The foamable liquid resin composition of the present invention contains a lubricant (E). By containing the lubricant (E), it is possible to reduce friction and adhesion in the foam cell of the foam formed by foaming the foamable liquid resin composition, and to obtain a foam having a desired tactile sensation and flexibility. it can. Further, the lubricant (E) is held in the three-dimensional network structure formed by the hydrosilylation reaction of the curing agent (A-1) and the curing agent (A-2) and the polymer (B), and foamed. Since bleed-out outside the system tends to be suppressed, it is possible to maintain tactile sensation and flexibility over a long period of time.

  The lubricant (E) of the present invention is preferably a liquid lubricant. Specific examples of liquid lubricants include animal and vegetable oils such as paraffinic mineral oils, naphthenic mineral oils and fatty acid glycerides; olefinic lubricants having an alkyl structure such as poly-1-decene and polybutene; alkyl aromatics having an aralkyl structure Compound lubricants; polyalkylene glycol lubricants; ether lubricants such as polyalkylene glycol ethers, perfluoropolyethers, polyphenyl ethers; fatty acid esters, fatty acid diesters, polyol esters, silicate esters, phosphate esters, etc. Ester-based lubricant having an ester structure; dimethyl silicone (that is, dimethylpolysiloxane blocked with trimethylsiloxy groups at both ends), and a part of methyl groups of dimethylsilicone are polyether groups, phenyl groups, alkyl groups, aralkyl groups, Silicone lubricant such as substituted silicone oil in Tsu fluorinated alkyl group or the like; a fluorine atom-containing lubricant such as chlorofluorocarbon and the like.

  Among these, in the present invention, a silicone-based lubricant is particularly preferable from the viewpoints of reduction in coefficient of friction in the foamed cell, dispersibility, workability, safety, and the like.

The lubricant (E) in the present invention has a kinematic viscosity at 25 ° C. of 10,000 mm ² / s or less, more preferably 15000 mm, from the viewpoint of the effect of lowering the coefficient of friction in the foamed cell and the tactile flexibility of the resulting foam. ^It is preferably ² / s or less, more preferably 7000 mm ² / s or less, and particularly preferably 5000 mm ² / s or less.

In addition, the lubricant (E) has less lubricant bleed out from the obtained foam, and has a kinematic viscosity at 25 ° C. of 30 mm ² / s or more, more preferably 35 mm ^{2 in} terms of the feel and flexibility of the foam. / S or more, more preferably 40 mm ² / s or more. In addition, 1 type may be used for the lubricant (E) in this invention, and 2 or more types may be used for it in arbitrary ratios and combinations. The kinematic viscosity at 25 ° C. can be measured with a Ubbelohde viscometer according to ASTM D 445-46T.

  In the present invention, the amount of the lubricant (E) added is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and still more preferably 3 parts by weight or more with respect to 100 parts by weight of the polymer (B). When the addition amount of the lubricant is small, the suppression of friction and adhesion in the foam cell becomes insufficient, and it is difficult to obtain desired tactile sensation and flexibility. The upper limit of the lubricant is not particularly limited, but is preferably 22 parts by weight or less, and more preferably 20 parts by weight or less. When the amount is too large, the foaming ratio of the foam tends to decrease, or the lubricant bleeds out.

-About the plasticizer (F) The foamable liquid resin composition of the present invention has an average of less than one alkenyl group in the molecular chain, and the repeating unit constituting the main chain is an oxyalkylene unit. (F) is contained. By containing a plasticizer (F), the softness | flexibility of a foam can be adjusted, suppressing the bleed-out from the foam formed by foaming a foamable liquid resin composition.

  The plasticizer (F) in the present invention has an average of less than 1 alkenyl group in the molecular chain. Preferably, it does not have an alkenyl group in the molecular chain. If it is a plasticizer having an average of less than one alkenyl group in the molecular chain, the curing reaction between the curing agent (A) and the polymer (B) is hardly inhibited, and poor curing hardly occurs. Other functional groups may be included to some extent as long as they hardly inhibit the curing reaction between the curing agent (A) and the polymer (B). Examples of such functional groups include hydroxyl groups, amino groups, carboxyl groups, isocyanate groups and the like.

  In the plasticizer (F) in 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 (F) in the present invention is 1000 or more as the number average molecular weight from the viewpoint of flexibility of the foam formed by foaming the foamable liquid resin composition and prevention of outflow of the plasticizer out of the system. Furthermore, 3000 or more are preferable. If the number average molecular weight of the plasticizer is low, 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 is deteriorated. Therefore, 30000 or less is preferable, and 25000 or less is more preferable.

  The plasticizer of the present invention is not particularly limited as long as it can impart flexibility to the modified silicone resin foam, whether linear or branched.

  The addition amount of the plasticizer in the present invention is preferably 5 parts by weight or more and 90 parts by weight or less, more preferably 6 parts by weight or more and 85 parts by weight or less, and more preferably 7 parts by weight or more and 80 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 small, the effect of imparting flexibility may be insufficient. When the amount is too large, the mechanical strength of the modified silicone resin foam is insufficient, and the foam tends to shrink.

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

  ・ About other additives.

  As long as the effects of the present invention are not impaired, the foamable liquid resin composition of the present invention may be added with a light-resistant stabilizer, an ultraviolet absorber, a storage stabilizer, a cell regulator, a surfactant and the like as necessary. Also good.

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 to 10 ⁻¹ mol 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 the amount exceeds 10 ⁻¹ mol, the curability becomes insufficient. There is.

  If necessary, a foam regulator may be added to the foamable liquid resin composition of the present invention. There are no particular limitations on the type of cell regulator, and examples of commonly used foaming agents include inorganic solid powders such as talc, calcium carbonate, magnesium oxide, titanium oxide, zinc oxide, carbon black, silica, and fluorine compounds. It is done. These may be used alone or in combination of two or more.

  In the present invention, the amount of the air bubble regulator used is preferably from 0.1 to 100 parts by weight, more preferably from 0.5 to 50 parts by weight, when the polymer (B) is 100 parts by weight. .

  In the present invention, a foamable liquid resin composition comprising a curing agent (A), a polymer (B), a hydrosilylation catalyst (C), a foaming agent (D), a lubricant (E), and a plasticizer (F). A surfactant can be added for the purpose of improving the compatibility.

  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, particularly for the purpose of improving the compatibility of the polymer (B) with the curing agent (A) and the lubricant (E), a silicone-based surfactant such as a polyoxyalkylene-polydimethylsiloxane block copolymer is used. An agent can also be added.

  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. Specific examples of the structure of polyoxyalkylene include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the terminal structure also includes hydroxyl group. 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, 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 foam The manufacturing method of a foam is a hardening | curing agent (A), a polymer (B), a hydrosilylation catalyst (C), a foaming agent (D), a lubricant (E), a plasticizer (F). If the foamable liquid resin composition containing the composition is cured and foamed, it can be produced without any particular limitation.

  As the 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), the lubricant (E), and the plasticizer (F) are used. However, it is preferable that the components in the foamable liquid resin composition are in a well-mixed state. The mixing order of the components is not particularly limited, but after the polymer (B), hydrosilylation catalyst (C), blowing agent (D), and plasticizer (F) are mixed in advance, the curing agent (A) and the lubricant are mixed. It is preferable to produce a foamable liquid resin composition by mixing (E).

  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 with good balance, and a preferred foam of the present invention is obtained.

  There is no particular limitation on the time for maintaining the temperature (heating time), but it is maintained at a temperature of 5 minutes to 3 hours, further 10 minutes to 2.5 hours, particularly 20 minutes to 2 hours. A preferred foam of the present invention is obtained.

  Furthermore, since the obtained foam tends to be able to reduce compressive residual strain, it is preferable to perform heat curing. The heating curing conditions are not particularly limited, but the heating temperature conditions are preferably 40 ° C to 200 ° C. In addition, it is preferable to perform the heat curing under a condition of 10 minutes to 72 hours because the compression residual strain is reduced.

  The compression residual strain of the foam obtained by foaming the foamable liquid resin composition of the present invention can be made into a foam of 10% or less, further 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. The compressive residual strain in the present invention is based on JIS K 6400-4. The foam is compressed 75% and heated at 40 ° C. for 8 hours, and then the compression is released at room temperature. The rate of decrease with respect to the thickness.

The foam obtained by foaming the foamable liquid resin composition of the present invention is preferably a foam having a density of 350 kg / m ³ or less, more preferably 320 kg / m ³ or less, and further 300 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. However, if a strong and preferable value is exemplified, it is preferably 20 kg / m ³ or more, more preferably 30 kg / m ³ or more, and further 40 kg / m ^3. In particular, 50 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 foam obtained by foaming the foamable liquid resin composition of the present invention has a hardness on a tofu hardness meter (manufactured by Oba Keiki Seisakusho Co., Ltd.) at 25 ° C. of 0.80 N or less, more preferably 0.8. It is also possible to form a foam which is 50 or less, further 0.30 or less, particularly 0.25 or less.

The foam obtained by foaming the foamable liquid resin composition of the present invention preferably has a hardness per unit density of 1.00 mN / (kg / m ³ ) or less, more preferably 0.95 mN / It is preferably (kg / m ³ ) or less, more preferably 0.90 mN / (kg / m ³ ) or less. If it is the said range, it can be said that it is a foam excellent in the softness | flexibility. In addition, the hardness per unit density in this invention is the value which remove | divided the hardness using the hardness meter for tofu by a density.

  Although it does not specifically limit as a form of the foam of this invention, For example, what was shape | molded in the shape of a plate shape, a sheet shape, an indeterminate lump shape, a bead shape, or a bag shape or clothes, etc. are mentioned. 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 foam of the present invention using an adhesive. By sticking together in this way, it is possible to further improve the touch of the foam, or to apply a sweat absorbing action by the bonded fabric during exercise or sweating at high temperature and high humidity.

  Although it does not specifically limit as a shape of the foam of this invention, Polygons, such as a rectangle, a square, a circle, an ellipse, a rhombus, what gave arbitrary unevenness | corrugations to the surface, etc. are mentioned. Moreover, you may make a through-hole suitably in order to give air permeability.

  The foam of the present invention does not use isocyanate, has good tactile sensation and flexibility, and has a small compressive residual strain, so it can be used for various applications such as soundproofing materials, vibration damping materials, and cushioning materials. It is. Specifically, it can be suitably used for applications such as transportation equipment, bedding / bedding, furniture, various equipment, toiletries, footwear, various miscellaneous goods, clothing, sports equipment, toys / playground equipment, building materials, packaging materials, medical care / nursing care.

  As an application that can effectively exhibit the excellent tactile sensation and flexibility of the foam of the present invention, for example, as a transportation equipment application, a seat of an automobile, a construction machine, a railway vehicle, a ship, an aircraft, a child seat, a headrest, an armrest, a footrest, Headliner, saddle / rider cushions for motorcycles / bicycles, bed mats for custom cars, cushion materials such as camper cushions, skin / skin lining materials, ceiling materials, handles, door trims, instrument panels, dashboards, door panels Pillars, console boxes, quarter trims, sun visors, flexible containers, front mirrors, harnesses, dust covers and other core materials, skin / skin lining materials, floor cushions and other vibration-absorbing and sound-absorbing materials, helmet linings, crash pads, Cushioning material, such as a printer Pila garnish, energy absorbing bumpers, guard acoustic insulation, vehicle wax sponge, and the like.

Examples of bedding / bedding products include pillows, comforters, mattresses, beds, mattresses, bed mats, bed pads, cushions, cribs, baby neck pillows, and skin / skin lining materials.
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.

  Sporting goods include sports protectors, bouldering (climbing / mini-climbing climbing rocks with a height of about 2 to 3m), beat boards, cushions for high jump, landing mats for gymnastics and exercise, kids Examples thereof include cushion materials such as mats, skin materials, skin lining materials, liners for 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. .

  For medical / care applications, cell sheets for regenerative medicine, artificial skin, artificial bone, artificial cartilage, artificial organs, other biocompatible materials, chemical solution exuding pads, hemostatic pads, gas-liquid separation filters (indwelling needle filters), patching Agent, medical liquid absorbing device, mask, compression pad, surgical disposable product, electrode pad for low frequency treatment device, bed slip prevention mattress, posture change cushion, wheelchair cushion, wheelchair seat, shower chair and other care products, bathing Pillow for care, palm protector for contracture, taping, cast liner, prosthetic and prosthetic liner, case, tooth base, etc. Dental article, shock absorbing pad, hip protector, elbow / knee protector, wound dressing, etc. Can also be used.

  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. Note that “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified in the synthesis examples and composition preparations.

<Foam density>
A cube having a size of about 30 mm square was cut out from the obtained foam, the volume was calculated by measuring the size of three sides, and the density was calculated by removing it from the measured weight. In addition, the foam was contracted after the foam was produced, and those whose density could not be measured were described as “shrinkage”.

<Tactile sense>
The tactile sensation when the obtained foam was compressed by hand was evaluated according to the following criteria, and passed with Δ or higher.

○: When the finger is pushed down until it feels bottoming, it can be laterally deformed with a small force (equivalent to a gel material).
○ △: Pushing with your finger until you feel a bottom feeling, and when you move it to the side, you can deform with a moderate force. A large force is required for shear deformation. △ ×: Push until you feel a bottom feeling with your finger, and when it is shifted to the side, if you apply a large force, you can perform a lateral shear deformation, but the amount of deformation is small. When you push it until you feel a bottom, and then move it to the side, you will not be able to deform sideways even if you apply a large force.

<Bleed out>
The obtained foam was touched by hand, and the presence or absence of adhesion of the bleed product to the hand was evaluated according to the following criteria.

◯: No bleed adherence △: Slightly bleed adherence △: Slightly bleed adherence △: Bleed adherence ×: A large amount of bleed adherence

<Hardness / Hardness change rate>
The obtained foam was cut into a 30 mm square cube, and the hardness after foam production was evaluated using a tofu hardness meter (manufactured by Oba Keiki Seisakusho Co., Ltd.) as a measure of flexibility. Moreover, after performing heat curing for 1 week in the oven set to 100 degreeC, the hardness after heat curing was evaluated using the hardness meter for tofu,
Hardness change rate (%) = (Hardness after heat curing−Hardness after foam production) / Hardness after foam production × 100
The hardness change rate was calculated from the formula:

<Hardness per unit density>
The hardness per unit density was calculated by dividing the hardness measured with a tofu hardness tester by the density.

<Compressive residual strain>
In accordance with JIS K 6400-4 C method, the obtained foam was cut into a 30 mm square cube, compressed to 75% (until 7.5 mm thickness), and heated in an oven at 40 ° C. for 8 hours. did. Thereafter, the film was taken out and released from compression at room temperature. The thickness after 30 minutes was measured to calculate the rate of decrease in thickness with respect to the original thickness.

<Compressive residual strain (30 times)>
In order to evaluate the repeated change of the compressive residual strain, the above-described compressive residual strain was evaluated as one cycle, and this was repeated 30 times.

<Compressive residual strain and hardness change rate in actual use>
Width 400mm Depth 400mm Thickness 30mm Urethane Foam (ERG-H, manufactured by Inoac Corporation) 4 rows of 200mm x 200mm x 50mm foams produced in the example are arranged so that the width is 400mm and the depth is 400mm. A cushion material having a thickness of 80 mm was laid. The seating surface is a foam produced in the example. Cover this cushion material to make a cushion, and 6 subjects took a seating test where each person was seated on an office chair using the cushion material for approximately 6 hours to 12 hours a day, and measured the thickness and hardness of the cushion. The change rate of thickness and hardness was obtained. Here, the number of sitting days is the number of days that the subject has actually been seated. The hardness was measured according to JIS K 6400-2 A method, and the rate of change in hardness was calculated from the obtained hardness by the following formula.
Hardness change rate (%) = (hardness at each seating day−hardness at the start of evaluation) / hardness at the start of evaluation × 100.

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

(Synthesis of curing agent (A-2))
(-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 hydrosilyl group equivalent was 238 g / mol (compound 30% The amount of hydrogen generated by adding to ethanolic potassium hydroxide was measured with a WS-type wet gas meter, and the hydrosilyl group equivalent in the compound was estimated.)

(Synthesis of polymer (B))
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 double metal cyanide complex catalyst (zinc hexacyanocobaltate) to obtain a polymer having a number average molecular weight of 20000.

  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 polyoxypropylene polymer (polymer (B-1)) was obtained. The allyl group equivalent of the obtained polymer was measured (measured by titration of the amount of allyl group by a method according to JIS K 1557), and from the result, the alkenyl group contained in one molecule was 2.4. understood.

(Synthesis of plasticizer (F))
An oxypropylene polymer glycol having a number average molecular weight of 3000 was obtained by a polymerization method using caustic alkali. The resulting oxypropylene polymer glycol is used as an initiator to polymerize propylene oxide using a double metal cyanide complex catalyst (zinc hexacyanocobaltate), and a polymer having a number average molecular weight of 20000 having 0 alkenyl groups in one molecule. Got.

(Examples 1 to 10), (Comparative Examples 1 to 6)
In 100 parts of polymer (B) in a 1 L disposable cup, 1.0 part each of light-resistant stabilizer-1, light-resistant stabilizer-2, and ultraviolet absorber shown in Table 1, foaming agent (D) Each was added with 5.0 parts (weight ratio: baking soda / citric acid = 1) 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. Then, the hardening | curing agent (A) of Table 2, lubricant (E), and plasticizer (F) were mixed, and the foamable liquid resin composition was obtained.

  The obtained composition was injected into an iron mold (200 mm × 200 mm × 50 mm) coated with a fluororesin having an open top so that the thickness after curing of the foam was approximately 50 mm, and injected, It was cured by heating in an oven set at 100 ° C. for 60 minutes to obtain a foam. After removing the obtained foam from the mold and curing by heating in an oven set at 120 ° C. for 120 minutes, the density, touch, hardness, compression residual, and compression residual strain (30 times) of the foam were evaluated. . Further, as a change with time, the foam was subjected to heat curing in an oven set at 100 ° C. for 1 week, and the tactile sensation and hardness were evaluated. It shows in Table 2. In addition, the foam obtained in Example 5 was used for the rate of change in compression residual strain hardness in actual use. Table 3 shows the results.

  From Table 2 and Table 3, a curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol and a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less are used in combination. In addition, it can be seen that the foam obtained from the foamable liquid resin composition containing the lubricant (E) and the plasticizer (F) has a low bleed-out, and a foam having good touch and flexibility can be obtained.

  Further, when the hydrosilyl group content in the foamable liquid resin composition is 1.2 mol or more and 5.0 mol or less per mol of the alkenyl group, the resulting foam has a low compressive residual strain, and the tactile sensation due to change over time. It can be seen that there is no major change in flexibility and there is no problem with long-term use. In addition, since the 30-time compression residual strain is an evaluation at 40 ° C., which is higher than actual use, it is estimated that the compression residual strain is 5% or less even after one year from the start. In the evaluation in actual use, the hardness decreased by about 20% in about 30 days after the start of the evaluation, but has not changed substantially until 120 days have passed, and the compressive residual strain has not reached 120 days. Thus, a small state of about 3% can be maintained.

Claims (12)

A curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol to less than 180 g / mol, a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol to 700 g / mol, and having at least one alkenyl group. In addition, the polymer (B), the hydrosilylation catalyst (C), the foaming agent (D), the lubricant (E), and the repeating unit constituting the main chain consisting of an oxyalkylene unit, on average in the molecular chain A foamable liquid resin composition comprising a plasticizer (F) having an alkenyl group of less than 1 and a repeating unit constituting the main chain comprising an oxyalkylene-based unit, and containing the hydrosilyl group in the foamable liquid resin composition A foamable liquid resin composition having an amount of 1.1 to 5.0 moles per mole of alkenyl groups ,
The hydrosilyl group content of the curing agent (A-1) is 0.2 to 4.0 moles per mole of alkenyl groups, and the hydrosilyl group content of the curing agent (A-2) is 0 per mole of alkenyl groups. A foamable liquid resin composition having a molar ratio of 8 mol to 1.2 mol . The foamable liquid resin composition according to claim 1, wherein the polymer (B) has a number average molecular weight of 10,000 to 100,000. Polymer (B) of the foamable liquid resin composition of repeating units constituting the main chain according to 請 Motomeko 1 or 2 Ru oxypropylene der. The foamable liquid resin composition according to any one of claims 1 to 3, wherein the foaming agent (D) is a chemical foaming agent that decomposes by heating to generate an inorganic gas. The foamable liquid resin composition according to claim 1, wherein the lubricant (E) is a silicone-based lubricant having a kinematic viscosity (25 ° C.) of 30 mm ² / s to 10,000 mm ² / s. The foamable liquid resin composition according to any one of claims 1 to 5, wherein the plasticizer (F) has a number average molecular weight of 1,000 to 30,000. The foamable liquid resin composition according to any one of claims 1 to 6 , wherein the repeating unit constituting the main chain of the plasticizer (F) is oxypropylene. A curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol, a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less, and at least one in the molecular chain Polymer (B) having an alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene unit, hydrosilylation catalyst (C), blowing agent (D), lubricant (E), average in the molecular chain The foamable liquid resin composition according to any one of claims 1 to 7, comprising a plasticizer (F) having less than one alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene unit. A foam made by foaming a product. The foam according to claim 8, wherein the density is 20 kg / m ³ or more and 350 kg / m ³ or less. The foam according to claim 8 or 9, which has a compressive residual strain of 10% or less when 75% compressed at 40 ° C for 8 hours. A curing agent (A-1) having a hydrosilyl group equivalent of 30 g / mol or more and less than 180 g / mol, a curing agent (A-2) having a hydrosilyl group equivalent of 180 g / mol or more and 700 g / mol or less, and at least one in the molecular chain Polymer (B) having an alkenyl group and the repeating unit constituting the main chain comprising an oxyalkylene unit, hydrosilylation catalyst (C), blowing agent (D), lubricant (E), average in the molecular chain The foamable liquid resin composition comprising a plasticizer (F) having less than one alkenyl group and a repeating unit constituting the main chain comprising an oxyalkylene-based unit is foamed. The manufacturing method of the foam as described in any one of 10-10. The method for producing a foam according to claim 11, wherein the foamable liquid resin composition is cured and foamed at a temperature of 40 ° C. or higher and 150 ° C. or lower.