JP2009074041A - Foam and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foam which comprises, as a base resin, a silicone-based polymer flexible and having good touch feeling, and which does not use raw materials which may have toxicity. <P>SOLUTION: The main component of the base resin is a silicone-based polymer obtained by curing a liquid resin composition mainly comprising a hardener (A) having at least two hydrosilyl groups in the molecular chain, a polymer (B) which has at least one alkenyl group in the molecular chain and in which the repeating unit constituting the main chain is a saturated hydrocarbon unit or oxyalkylene unit, and a hydrosilylation catalyst (C), wherein the polymer (B) is a linear polymer having a number average molecular weight of 10,000 or higher. The foam comprises, as the base resin, the above silicone-based polymer. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a foam having a specific silicon-based polymer as a base resin.

  As foams of polymer compounds, foams using thermoplastic resins such as polystyrene, polyethylene, polypropylene, and polyvinyl chloride are used as beads, sheets, or boards, and have characteristics such as heat insulation, lightness, and buffering properties. It is used in the civil engineering and construction field, packaging field, home appliance field, and automobile field. All of these require a large-scale facility to form a molded body. These are also generally rigid foams.

  A polyurethane foam is well known as a foam using a thermosetting resin obtained by curing and foaming a liquid resin composition. Polyurethane foams can be easily molded with small-scale equipment, and soft foams can also be produced (Patent Document 1), but have the disadvantage of using isocyanates that are toxic. In addition, the polyurethane foam cannot be said to have sufficient flexibility and cannot be said to have a good tactile feel. Therefore, there is a demand for a foam that is easy to mold, flexible, and has good tactile sensation, without using a material that may be toxic.

  Examples of the foam made of a silicon-based polymer are disclosed in Patent Documents 2 to 4, for example. Patent Document 2 discloses a curing agent having at least two hydrosilyl groups in a molecular chain, at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain is a saturated hydrocarbon unit or oxyalkylene A composition for a roller having a foamed elastic body layer containing a polymer comprising a system unit, a hydrosilylation catalyst, and a conductivity imparting substance is disclosed, and has at least one alkenyl group in the molecular chain, What is substantially disclosed as a polymer in which the repeating unit constituting the main chain is composed of a saturated hydrocarbon unit or an oxyalkylene unit is an example in which a polymer having a number average molecular weight of 8000 is used. The hardness of the foam to be obtained is evaluated by the ASKER C hardness, and it is difficult to say that the foam is sufficiently soft.

Patent Document 3 discloses a foaming property comprising an organic compound having a carbon-carbon double bond and not containing a siloxane unit in a molecular skeleton, a compound having SiH having a specific chemical structure, and a compound having an OH group. A resin composition is disclosed, and a hard to soft silicon polymer foam obtained from the foamable resin composition is disclosed, but the hardness of the soft silicon polymer is not disclosed, In order to produce a foam having a desired hardness, any formulation, in particular, having at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain is a saturated hydrocarbon-based unit or an oxy There is no description or suggestion as to whether a polymer comprising an alkylene-based unit should be used. Patent Document 4 discloses a silicon-based foamable resin composition, but discloses obtaining a foam without using a foaming agent.
JP 2006-131754 A JP-A-8-267612 Japanese Patent Laid-Open No. 10-87995 JP 2000-351863 A

  In view of the above, an object of the present invention is to provide a foam that is flexible and has a good tactile sensation without using a raw material that may be toxic.

  As a result of intensive studies for solving the above problems, the present inventors have found that a curing agent having at least two hydrosilyl groups in the molecular chain, at least one alkenyl group in the molecular chain having a specific molecular weight. And a silicon-based resin obtained by curing a foamable resin composition comprising a polymer in which the repeating unit constituting the main chain is a saturated hydrocarbon-based unit or an oxyalkylene-based unit, a hydrosilylation catalyst, and a foaming agent The present inventors have found that the polymer foam is flexible and has good tactile sensation, and have completed the present invention.

  That is, the first of the present invention is a curing agent (A) having at least two hydrosilyl groups in the molecular chain, at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain is saturated. A foamable resin composition comprising a linear polymer (B) comprising a hydrocarbon-based unit or an oxyalkylene-based unit and having a number average molecular weight of 10,000 or more, a hydrosilylation catalyst (C), and a foaming agent (D). The present invention relates to a cured silicone polymer foam.

As a preferred embodiment (1) the repeating unit constituting the main chain of the polymer (B) is oxypropylene,
(2) The curing agent (A) / the polymer (B) (mol / mol) is 1/2 or more.
(3) The polymer (B) is a linear polymer having a number average molecular weight of 15000 or more.
(4) ASKER FP hardness is 50 or less,
(5) The foaming agent (D) is an active hydrogen group-containing compound.
The present invention relates to the silicon polymer foam described above.

  The second of the present invention is a method for producing a silicon-based polymer foam, which comprises a curing agent (A) having at least two hydrosilyl groups in the molecular chain and having at least one alkenyl group in the molecular chain. And a resin composition comprising a linear polymer (B) having a number average molecular weight of 10,000 or more, a hydrosilylation catalyst (C), wherein the repeating unit constituting the main chain is a saturated hydrocarbon unit or an oxyalkylene unit. The present invention relates to a method for producing a silicon-based polymer foam as described above, wherein a foaming resin composition is added to a product to form a foamable resin composition, which is injected into a mold and cured.

  ADVANTAGE OF THE INVENTION According to this invention, the foam which is flexible and favorable in tactile sense can be provided, without using the raw material which is worried about toxicity.

  Hereinafter, the present invention will be described in more detail. The silicon-based polymer foam of the present invention is characterized in that a specific silicon-based polymer is used as a base resin, and it is possible to obtain a foam that is flexible and has good tactile sensation. Specifically, the curing agent (A) having at least two hydrosilyl groups in the molecular chain, at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain being a saturated hydrocarbon unit Alternatively, it is obtained by curing a foamable resin composition comprising a linear polymer (B) having a number average molecular weight of 10,000 or more, a hydrosilylation catalyst (C), and a foaming agent.

  In addition, a bubble adjusting agent, a filler, a storage stabilizer, a thickener and the like may be added as necessary as long as the effects of the present invention are not impaired. The foaming agent (D) is a curing agent (A) having at least two hydrosilyl groups in the molecular chain (hereinafter sometimes simply referred to as “curing agent (A)”), and at least in the molecular chain. A linear polymer (B) having a number average molecular weight of 10,000 or more, wherein the repeating unit constituting one main chain is a saturated hydrocarbon unit or an oxyalkylene unit (hereinafter simply referred to as “ It is preferable to mix with the resin composition containing the hydrosilylation catalyst (C).

  The curing agent (A) of the present invention has at least 2, preferably 3 or more hydroxyl groups in the molecular chain. The upper limit of the hydroxyl group is preferably 100, more preferably 70, and still more preferably 50. Since the molecular chain has a hydroxyl group in this way, each hydrosilyl group has at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain is a saturated hydrocarbon unit or an oxyalkylene unit. It is cured by reacting with an alkenyl group present in the molecular chain of the linear polymer (B) having a number average molecular weight of 10,000 or more. When the number of the hydrosilyl groups is less than 2, the curing rate when the foamable resin composition of the present invention is cured by the hydrosilylation reaction is slowed, resulting in poor curing. When the number of hydrosilyl groups is more than 100, the stability of the curing agent (A), that is, the stability of the foamable resin composition of the present invention may be deteriorated. The hydrosilyl group tends to remain in the cured resin composition and may cause cracks.

In the present invention, having one hydrosilyl group means having one SiH bond, and in the case of SiH ₂ , it has two hydrosilyl groups, but the number of H bonded to one Si. One is more preferable in terms of flexibility and also in terms of flexibility. In the present invention, “an average of one hydrosilyl group in a molecular chain” is obtained by multiplying the number of hydroxyl groups per gram by the number average molecular weight of the substance. In the present invention, the number of functional groups in the molecular chain is similarly calculated for functional groups other than hydrosilyl groups unless otherwise specified.

  The molecular weight of the curing agent (A) is preferably 30000 as the upper limit of the number average molecular weight (Mn) from the viewpoint of dispersibility of the foaming agent (D) component described later and processability of the resulting foam. 20000 is more preferable, and 15000 is more preferable. In consideration of the reactivity and compatibility with the polymer (B), the number average molecular weight is particularly preferably from 300 to 10,000.

  The structure of the curing agent (A) is not particularly limited as long as it has at least two hydrosilyl groups in the molecular chain, and examples thereof include hydrocarbon curing agents and polysiloxane curing agents.

The hydrocarbon curing agent is a general formula (1)
R ¹ X _a (1)
(X: a group containing at least one hydrosilyl group, R ¹ : a monovalent to tetravalent hydrocarbon group having 2 to 150 carbon atoms, a: an integer selected from 1 to 4, provided that only one hydrosilyl group is present in X If not included, a is 2 or more)
A preferred specific example is a hydrocarbon-based curing agent containing a hydrosilyl group having a number average molecular weight of 30000 or less.

Specific examples of the X, for _{example, -SiH n (CH 3) 3} -n, -SiH n (C 2 H 5) 3-n, -SiH n (C 6 H 5) 3-n ( or more n = 1 to 3), a hydrosilyl group containing only one silicon atom such as —SiH ₂ (C ₆ H ₁₃ ),

例えば、化１で示されるケイ素原子を２個以上含むヒドロシリル基、

For example, a hydrosilyl group containing two or more silicon atoms represented by chemical formula 1,

例えば、化２〜化４などで示される鎖状、枝分かれ状、環状の各種の多価ハイドロジェンシロキサンより誘導されたヒドロシリル基などが挙げられる。なお、式中、ｍ個の単位とｐ個の単位、ｎ個の単位とｑ個の単位、ｍ個の単位とｐ個の単位とｘ個の単位、ｎ個の単位とｑ個の単にとｙ個の単位、ｍ個の単位とｎ個の単位、さらにはｍ個の単位とｎ個の単位とｐ個の単位とｑ個の単位がブロック結合で結合しているように記載されているが、これらはブロック結合でもランダム結合でもよい。以下の記載においても同様である。

Examples thereof include hydrosilyl groups derived from various chain, branched, and cyclic polyvalent hydrogen siloxanes represented by chemical formulas 2 to 4. In the formula, m units and p units, n units and q units, m units and p units and x units, n units and q units, It is described that y units, m units and n units, and m units, n units, p units, and q units are connected by a block connection. However, these may be block bonds or random bonds. The same applies to the following description.

Of various hydrosilyl groups mentioned above, from the viewpoint that a curing agent (A) hydrocarbon-based curing agent is less likely to impair the compatibility with other organic polymers, general formula X _a (1) The molecular weight of the moiety is preferably 500 or less, and in view of the reactivity of the hydrosilyl group, the hydroxyl group represented by Chemical formula 5 is preferred.

一般式（１）中、Ｒ^１は炭素数２〜１５０で１〜４価の炭化水素基を表し、重合体からなる基であってもよい。重合体でない具体例としては、化６、化７に示すもの（これらは特開平３−９５２６６号公報などに記載されている）などが挙げられる。

In the general formula (1), R ¹ represents a 1 to 4 valent hydrocarbon group having 2 to 150 carbon atoms, and may be a group composed of a polymer. Specific examples which are not polymers include those shown in Chemical formulas 6 and 7 (these are described in JP-A-3-95266).

また、重合体からなるＲ^１基の具体例としては、エチレン、プロピレン、１−ブテン、イソブチレンなどのような炭素数２〜６のオレフィン系化合物を主モノマーとして重合させたもので、結合手を１〜４個有するもの、ブタジエン、イソプレンなどのようなジエン系化合物を単独重合させたり、前記オレフィン系化合物とジエン系化合物とを共重合させた後、水素添加したもので、結合手を１〜４個有するものなどが挙げられる。

Further, specific examples of the R ¹ group made of a polymer are polymers obtained by polymerizing olefinic compounds having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like as main monomers. One having 1 to 4 diene compounds such as butadiene, isoprene or the like, copolymerized the olefin compound and diene compound, and then hydrogenated. The thing which has four is mentioned.

Among the hydrocarbon-based curing agents, the combination in the case where R ¹ is a hydrocarbon group having 5 to 20 carbon atoms and X is a group represented by Chemical Formula 5 increases the reactivity and takes a good network structure. And from the viewpoint of compatibility with the polymer (B). In addition, from the viewpoint of easy availability of raw materials, among these, a hydrocarbon group having 5 to 12 carbon atoms in R ¹ is more preferable, and the compatibility with the polymer (B) is particularly improved. From the above, it is more preferable that X is a cyclic polysiloxane compound among the groups represented by formula 5. A compound obtained by this combination is preferable as the hydrocarbon-based curing agent. Specific examples thereof include those shown in Chemical formula 8 below.

炭化水素系硬化剤の製法については特に制限はなく、任意の方法で製造すればよい。例えば、（ｉ）分子中にＳｉＣｌ基を持つ炭化水素系化合物をＬｉＡｌＨ_４、ＮａＢＨ_４などの還元剤で処理して該化合物中のＳｉＣｌ基をＳｉＨ基に還元する方法、（ｉｉ）分子内にある官能基Ｘ^１を持つ炭化水素系化合物と分子内に前記官能基Ｘ^１と反応する官能基Ｙ^１およびヒドロシリル基の両者を有する化合物とを反応させる方法、（ｉｉｉ）アルケニル基を含有する炭化水素系化合物に対して少なくとも２個のヒドロシリル基を持つポリヒドロシラン化合物を選択ヒドロシリル化することにより、反応後もヒドロシリル基を該炭化水素系化合物の分子中に残存させる方法、などが例示される。前記方法のうち、製造工程が一般に簡便なことから（ｉｉｉ）の方法が好適に用いられる。この場合、一部のポリヒドロシラン化合物に含まれるヒドロシリル基の２個以上が、炭化水素系化合物中のアルケニル基と反応して分子量が増大することがあるが、このように、分子量が増大したものを含むものを硬化剤（Ａ）として用いても何ら差し支えない。

There is no restriction | limiting in particular about the manufacturing method of a hydrocarbon type hardening | curing agent, What is necessary is just to manufacture by arbitrary methods. For example, (i) a method in which a hydrocarbon compound having a SiCl group in the molecule is treated with a reducing agent such as LiAlH ₄ or NaBH ₄ to reduce the SiCl group in the compound to a SiH group, (ii) a method of reacting a compound having both a functional group Y ¹ and a hydrosilyl group reactive with the functional groups X ¹ to a hydrocarbon compound having a functional group X ¹ and the molecule, carbide containing (iii) an alkenyl group Examples thereof include a method of selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to a hydrogen compound so that the hydrosilyl group remains in the molecule of the hydrocarbon compound after the reaction. Among the above methods, the method (iii) is preferably used because the production process is generally simple. In this case, two or more of the hydrosilyl groups contained in some polyhydrosilane compounds may react with the alkenyl group in the hydrocarbon compound to increase the molecular weight. In this way, the molecular weight is increased. There is no problem even if a material containing is used as the curing agent (A).

  A polysiloxane curing agent can also be used as the curing agent (A). Specific examples include linear and cyclic polyorganohydrogensiloxanes as shown in Chemical Formula 9 to Chemical Formula 11 including polyoxyalkylene-modified products, styrene-modified products, and olefin-modified products.

（ｍ、ｎ：２≦ｍ＋ｎ≦１００、２≦ｍ、０≦ｎを満たす整数、Ｒ：メチル基、分子量が１００〜１００００のポリオキシアルキレン基または炭素数２〜２０の炭化水素基で１個以上のフェニル基を含有していてもよく、Ｒが複数個含まれる場合、これらは同じでなくともよい。）

(M, n: 2 ≦ m + n ≦ 100, 2 ≦ m, integer satisfying 0 ≦ n, R: methyl group, one polyoxyalkylene group having a molecular weight of 100 to 10,000 or hydrocarbon group having 2 to 20 carbon atoms) The above phenyl group may be contained, and when a plurality of Rs are contained, these may not be the same.)

（ｍ、ｎ：２≦ｍ＋ｎ≦１００、０≦ｍ、０≦ｎを満たす整数、Ｒ：メチル基を基本とし、分子量が１００〜１０，０００のポリオキシアルキレン基または炭素数２〜２０の炭化水素基で１個以上のフェニル基を含有していてもよく、Ｒが複数個含まれる場合、これらは同じである必要はない。）

(M, n: an integer satisfying 2 ≦ m + n ≦ 100, 0 ≦ m, 0 ≦ n, R: a polyoxyalkylene group based on a methyl group and having a molecular weight of 100 to 10,000 or carbonization having 2 to 20 carbon atoms The hydrogen group may contain one or more phenyl groups, and when a plurality of Rs are contained, these need not be the same.)

（ｍ、ｎ：３≦ｍ＋ｎ≦２０、２≦ｍ≦１９、０≦ｎ≦１８を満たす整数、Ｒ：メチル基、分子量が１００〜１０，０００のポリオキシアルキレン基または炭素数２〜２０の炭化水素基で１個以上のフェニル基を含有していてもよく、Ｒが複数個含まれる場合、これらは同じである必要はない。）
重合体（Ｂ）との相溶性をより良くするためには、化９〜１１の内、Ｒがフェニル基を含有しているものが好ましい。さらに入手のしやすさからＲは、―ＣＨ_２―ＣＨ_２―Ｃ_６Ｈ_５、―ＣＨ_２―ＣＨ（ＣＨ_３）―Ｃ_６Ｈ_５、また、貯蔵安定性の点から―ＣＨ_２―ＣＨ（ＣＨ_３）―Ｃ_６Ｈ_５であることが好ましい。

(M, n: 3 ≦ m + n ≦ 20, 2 ≦ m ≦ 19, integer satisfying 0 ≦ n ≦ 18, R: methyl group, polyoxyalkylene group having a molecular weight of 100 to 10,000, or having 2 to 20 carbon atoms (The hydrocarbon group may contain one or more phenyl groups, and when a plurality of Rs are contained, these need not be the same.)
In order to improve the compatibility with the polymer (B), it is preferable that R in formula 9 to 11 contains a phenyl group. In addition, R is —CH ₂ —CH ₂ —C ₆ H ₅ , —CH ₂ —CH (CH ₃ ) —C ₆ H ₅ , and —CH ₂ —CH from the viewpoint of storage stability. (CH ₃ ) —C ₆ H ₅ is preferred.

  The polymer (B) in the present invention has at least one alkenyl group in the molecular chain, the repeating unit constituting the main chain is a saturated hydrocarbon unit or an oxyalkylene unit, and the number average molecular weight Is preferably a linear polymer having a molecular weight of 10,000 or more. 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 alkenyl groups contained in the polymer (B) is at least one from the viewpoint of hydrosilylation reaction with the curing agent (A). From the viewpoint of curability and flexibility, both ends of the molecular chain are required. Preferably an alkenyl group is present. Here, the term “linear” refers to a linear polymer if the molecular structure is linear or may be branched to some extent, and if the branch is less than the molecular weight of the main chain.

As the molecular weight of the polymer (B), when the repeating unit constituting the main chain is composed of a saturated hydrocarbon-based unit, the number average molecular weight is 10,000 in terms of the flexibility, feel and ease of handling of the obtained foam. About 50,000 is preferable, and more preferably about 15,000 to 30,000 liquid material to fluidity. As described above, the main chain in the case where the repeating unit constituting the main chain of the polymer (B) is composed of a saturated hydrocarbon unit,
(1) Polymerization using an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a main monomer,
(2) After homopolymerizing a diene compound such as butadiene or isoprene or copolymerizing the olefin compound and the diene compound, hydrogenation,
However, it is easy to introduce a functional group at the terminal, to easily control the molecular weight, and to increase the number of terminal functional groups, so that an isobutylene polymer or a hydrogenated polybutadiene system can be obtained. A polymer or a hydrogenated polyisoprene polymer is preferred. In the present invention, the saturated hydrocarbon polymer (such as an isobutylene polymer) means a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring.

  In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units having copolymerizability with isobutylene are preferably 50% by weight or less of the isobutylene polymer, more preferably. May be contained in a range of 30 wt% or less, more preferably 10 wt% or less. Examples of the monomer component copolymerizable with isobutylene include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and acrylic silanes. Specific examples of such a copolymer component include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, and vinylcyclohexane. , Methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyl trichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinylmethylmethoxysilane, Vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, Ryltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Silane etc. are mentioned. Among the monomer components copolymerizable with isobutylene, compounds other than the compound containing an alkoxysilyl group are preferable because of easy copolymerization.

  In the hydrogenated polybutadiene-based polymer and hydrogenated polyisoprene-based polymer, as in the case of the isobutylene-based polymer, in addition to the monomer unit as the main component, other monomers as described above are used. Units may be included.

  In the saturated hydrocarbon polymer used as the polymer (B), a single amount such as a polyene compound such as butadiene or isoprene, in which a double bond remains after polymerization, remains within the scope of achieving the object of the present invention. The body unit may be contained in a small amount, preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 1% by weight or less.

  As a method for introducing an alkenyl group into a main chain composed of saturated hydrocarbon units to obtain a polymer (B), various known methods can be used, but a method of introducing an alkenyl group after polymerization can be used. And a method of introducing an alkenyl group during the polymerization.

As a method for introducing an alkenyl group after polymerization, for example, a terminal, main chain or side chain hydroxyl group is changed to a group such as —ONa or —OK, and then the general formula (2):
CH ₂ = CH—R ² —Y (2)
(Y: halogen atom such as chlorine atom, bromine atom, iodine atom, R ² : —R ³ —, —R ³ —OCO—, or —R ³ —CO— (R ³ : 2 having 1 to 20 carbon atoms) A divalent organic group represented by an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group, as preferred specific examples, and a compound represented by Chemical Formula 12 (R ⁴ : having 1 to 10 carbon atoms). Divalent groups selected from hydrocarbon groups) are particularly preferred)

で示される有機ハロゲン化合物を反応させることにより、末端、主鎖または側鎖にアルケニル基を有する飽和炭化水素系重合体が製造できる。前記飽和炭化水素系重合体の好ましい具体例としては、両末端にアルケニル基を２個有する直鎖状の数平均分子量（Ｍｎ）が１００００〜２００００で重量平均分子量（Ｍｗ）と数平均分子量の比Ｍｗ／Ｍｎが１．１〜１．２程度のポリイソブチレン、水添ポリブタジエン、水添ポリイソプレン系重合体などが挙げられる。

A saturated hydrocarbon polymer having an alkenyl group at the terminal, main chain or side chain can be produced by reacting the organic halogen compound represented by formula (1). As a preferable specific example of the saturated hydrocarbon polymer, a linear number average molecular weight (Mn) having two alkenyl groups at both ends is 10,000 to 20000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight. Examples thereof include polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene-based polymer having Mw / Mn of about 1.1 to 1.2.

  As the molecular weight of the polymer (B) in which the repeating unit constituting the main chain is an oxyalkylene-based unit, the number average molecular weight (Mn) is 10,000 or more from the viewpoint of the balance between flexibility, touch and reactivity, Preferably it is 12000 or more, More preferably, it is 15000 or more. The upper limit is not particularly limited, but is preferably 50000 or less, more preferably 30000 or less, and even more preferably 25000.

When the repeating unit constituting the main chain of the polymer (B) is an oxyalkylene unit, a compound having two or more active hydrogens as a starting material for forming the main chain, such as ethylene glycol, propylene glycol, bisphenol compound, It is produced by polymerizing a C _{2 to} C ₄ alkylene oxide using glycerin, trimethylolpropane, pentaerythritol or the like. Specific examples of the polymer (B) in which the repeating unit constituting the main chain is an oxyalkylene unit include two or more kinds of random or block of polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide, propylene oxide and butylene oxide. A copolymer etc. are mentioned, It is more preferable to introduce | transduce an alkenyl group at least 1 type of terminal chosen from those groups similarly to the case of a saturated hydrocarbon type polymer (B).

  As a preferred specific example of the polymer (B) in which the repeating unit constituting the main chain is an oxyalkylene unit, the main chain repeating unit is preferably oxypropylene from the viewpoint of flexibility and touch.

  In the silicon polymer foam of the present invention, the content ratio of the curing agent (A) and the polymer (B) is also the number of hydrosilyl groups in the curing agent (A) and the number of alkenyl groups in the polymer (B). However, from the viewpoint of flexibility and touch, the curing agent (A) is preferably contained in a molar ratio of 1/2 or more, more preferably 3/4 or more, relative to the polymer (B). It is more preferable to contain 4/5 or more.

  Furthermore, the content of the hydrosilyl group in the curing agent (A) is preferably 0.1 to 50 mol per mol of the alkenyl group in the polymer (B), and is preferably 0.2 to 30 mol. More preferably.

The hydrosilylation catalyst (C) of the present invention is not particularly limited as long as it can be used as a hydrosilylation catalyst, and any catalyst can be used. Specific examples of the hydrosilylation catalyst (C) include a platinum support; a support such as alumina, silica, and carbon black, on which solid platinum is supported; chloroplatinic acid; chloroplatinic acid and alcohol, aldehyde, ketone, and the like. complex; _{e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) 2, Pt platinum such as _{(CH 2 = CH 2) 2} Cl 2 - olefin complexes; for _{example, Pt n (ViMe 2 SiOSiMe 2} Vi) m, Platinum-vinylsiloxane complexes such as Pt [(MeViSiO) ₄ ] _m ; for example, platinum-phosphine complexes such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; for example, Pt [P (OPh) ₃ ] ₄ , Platinum-phosphite complexes such as Pt [P (OBu) ₃ ] ₄ ; and dicarbonyldichloroplatinum. In the above formula, Me: methyl group, Bu: butyl group, Vi: vinyl group, Ph: phenyl group, m, n: an integer of 1 or more.

Also, the platinum-hydrocarbon composite described in US Pat. No. 3,159,601 to Ashby and US Pat. No. 3,159,662, US Pat. No. 3 to Lamoreaux. , 220,972, the platinum alcoholate catalyst described in Modic, and the chloroplatinic acid-olefin complex described in US Pat. No. 3,516,946 of Modic are also useful in the present invention. Can do. Furthermore, catalysts other than platinum compounds can be used. Specific examples thereof include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al 2 O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl _2. 2H ₂ O, NiCl ₂ , TiCl _{2 and the} like (Ph represents a phenyl group). It is preferable to use at least one selected from the hydrosilylation catalyst group mentioned above as the hydrosilylation catalyst (C). Among them, chloroplatinic acid, a platinum-olefin complex, and a platinum-vinylsiloxane complex are preferable from the viewpoint of catalytic activity and safety.

As content of a hydrosilylation catalyst (C), 10 ^<-8 > ^-10 < ^-1 > mol is preferable with respect to 1 mol of alkenyl groups of a polymer (B), and 10 ^<-6 > ^-10 <^-3> mol is more preferable. If the content is less than 10 ⁻⁸ mol, curing may not proceed sufficiently. Moreover, when there are more than 10 ^<-1> mol, the control of hardening of a resin composition may be difficult, and the obtained foam may color.

  Although it does not specifically limit as a foaming agent (D) of this invention, A gas, a liquid, and a solid foaming agent are mentioned at normal temperature (23 degreeC). In addition, when the blowing agent is classified in another aspect, for example, a volatile liquid or gaseous physical foaming agent usually used for organic foams such as polyurethane, phenol, polystyrene, polyolefin, etc., gas is generated by thermal decomposition or chemical reaction. Examples thereof include chemical foaming agents to be generated and active hydrogen group-containing compounds that react with hydrosilyl groups to generate hydrogen. Among these, the active hydrogen group-containing compound is preferably used because it contributes to improvement of open cell ratio and expression of physical properties such as flexibility. Moreover, as a foaming agent (D), at least 1 sort (s) chosen from a physical foaming agent, a chemical foaming agent, and an active hydrogen compound can be used.

  The physical foaming agent is not particularly limited as long as it does not inhibit the hydrosilylation reaction, but from the viewpoint of foamability, workability and safety, the physical foaming agent has a boiling point of 100 ° C. or less. Preferably, 50 degrees C or less is more preferable. 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. Of these, hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2 , 3-dimethylbutanecrobutane, cyclopentane, cyclohexane and the like.

  The 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 ether. Etc. In addition, when performing mechanical stirring in the air at the time of foam manufacture, air bubbles may be formed by the air entrained with the stirring, which is also considered to be one of physical foaming agents. However, when these physical foaming agents are used, there are concerns about changes in physical properties after foam molding due to the residue, etc., and therefore by heating and curing at a temperature equal to or higher than the boiling point of the used physical foaming agent after foam production. It is preferable to remove the residual foaming agent.

The chemical foaming agent is not particularly limited as long as it does not inhibit the hydrosilylation reaction, and examples thereof include inorganic chemical foaming agents such as NaHCO ₃ and organic chemical foaming agents.

  The active hydrogen group-containing compound is not particularly limited as long as it is a compound containing an active hydrogen group that reacts with a hydrosilyl group to generate hydrogen, and the following can be exemplified. That is, examples of the active hydrogen-containing compound include alcohols, carboxylic acids, compounds having a phenolic hydroxyl group, and water. Specific examples include water;

Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Monohydric alcohols such as ethylene glycol monophenyl ether, ethylene glycol monoallyl ether, glyceryl diallyl ether;

Ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 1,9-nona Polyhydric alcohols such as methylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, glyceryl monoallyl ether;

Polyether polyols including polypropylene glycol, polyethylene glycol, copolymers thereof, polytetramethylene glycol, sorbitol, sucrose, tetraethylenediamine, ethylenediamine, etc. containing one or more hydroxyl groups in one molecule ;

Polyester polyols such as adipate polyols, polycaprolactone polyols, polycarbonate polyols;

Epoxy-modified polyols; polyether ester polyols; phenolic polyols such as benzylic ether type phenol polyols; fluorine polyols such as Lumiflon (Asahi Glass Co., Ltd.); polybutadiene polyols; hydrogenated polybutadiene polyols; castor oil-based polyols; halogen-containing flame-retardant polyols A phosphorus-containing flame retardant polyol;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, “Aronix 5700” manufactured by Toagosei Co., Ltd., 4-hydroxystyrene, “HE-10”, “HE-20”, “HP-10” and “HP-20” manufactured by Nippon Shokubai Chemical Industry Co., Ltd. [all of which are acrylic acid ester oligomers having a hydroxyl group at the terminal], Nippon Oil & Fats Co., Ltd. ) Made of PP series [polypropylene glycol methacrylate], BLEMMER PE series [polyethylene glycol monomethacrylate], BLEMMER PEP series [polyethylene glycol polypropylene glycol methacrylate], BLEMMER AP- 00 [polypropylene glycol monoacrylate], Blemmer AE-350 [polyethylene glycol monoacrylate], Blemmer NKH-5050 [polypropylene glycol polytrimethylene monoacrylate] and Blemmer GLM [glycerol monomethacrylate], hydroxyl group-containing vinyl compounds and ε- Hydroxyl group-containing vinyl monomers such as ε-caprolactone-modified hydroxyalkyl vinyl monomers obtained by reaction with caprolactone (note that hydroxyl group-containing vinyl monomers are either a curing agent (A) component or a foaming agent (D). A hydroxyl group obtainable by copolymerization of the hydroxyl group-containing vinyl monomer with acrylic acid, methacrylic acid, or a derivative thereof. Acrylic resin; other alkyd resins, resins having a hydroxyl group such as an epoxy resin;
Alcohols such as;

Carboxylic acids such as monovalent saturated carboxylic acids such as acetic acid and propionic acid; compounds having a phenolic hydroxyl group such as phenol, cresol, xylenol, resorcin, catechol, pyrogallol, bisphenol A, bisphenol B, bisphenol S, and phenol resin;
Etc.

  Among these active hydrogen group-containing compounds, from the viewpoint of reactivity and handleability, it is selected from the group consisting of primary saturated hydrocarbon alcohols such as methanol, ethanol, n-propanol, and n-butanol, polyether polyols, and water. In addition, from the viewpoint of imparting flexibility and moisture permeability, a compound in which oxygen is directly bonded to carbon or water is preferable. In particular, any of water, ethanol, and polyethylene glycol is preferable.

  The hydroxyl group equivalent in the active hydrogen group-containing compound in the present invention is preferably 0.1 mmol / g or more because the volume of the active hydrogen group-containing compound to be added increases and the expansion ratio is difficult to increase as the hydroxyl group equivalent decreases. Furthermore, 0.5 mmol / g or more is more preferable from the viewpoint of reactivity.

  In addition, when an active hydrogen compound having two or more hydroxyl groups or hydroxyl groups and alkenyl groups in one molecule such as polyethylene glycol or polyethylene glycol monoallyl ether is used as the foaming agent (D), a hydrosilyl group The reaction between the hydrosilyl group in the curing agent (A) and the hydroxyl group in the active hydrogen compound in the foaming agent (D) generates hydrogen gas and forms a crosslinked structure. Since the mechanical strength of the foam may be reduced, attention should be paid to the formulation as described below.

  In the present invention, when an active hydrogen group-containing compound having two or more hydroxyl groups or hydroxyl groups and alkenyl groups in one molecule is used as the foaming agent (D), the curing agent (A), polymer (B) and The blending ratio of the foaming agent (D) is appropriately selected depending on the structure of each compound, the target foaming ratio, and the target physical properties, and is not particularly limited, but the hydrosilyl group in the curing agent (A) is not particularly limited. The ratio of the number of moles: x to the sum of the number of moles of alkenyl groups in the polymer (B): y and the number of moles of hydroxyl groups in the blowing agent (D): z is x / (y + z) = 1 / It is preferably 10 to 50/1, more preferably x / (y + z) = 1/5 to 30/1, and further preferably x / (y + z) = 1/2 to 20/1. . If x / (y + z) exceeds 50/1, the crosslinking density may be low, and sufficient mechanical strength may not be obtained. If x / (y + z) is less than 1/10, sufficient foaming, Curing may not occur.

  Further, the ratio of the number of moles of alkenyl groups of the polymer (B): y and the number of moles of hydroxyl groups of the blowing agent (D): z is not particularly limited, and the desired foaming ratio, the desired physical properties, Although it can select suitably by the kind of frame | skeleton of a hardening | curing agent (A), and a foaming agent (D), generally y: z = 100: 1 to 1: 100 is preferable, and y: z = 10: 1-1: 20 is more preferable.

  The silicone-based polymer foam of the present invention may further include a filler, an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, polydimethylsiloxane-polyalkylene oxide, if necessary. Foam stabilizers such as organic surfactants or organic surfactants (polyethylene glycol alkylphenyl ether, etc.), acids or basic compounds (additives for adjusting the reaction between hydrosilyl groups and hydroxyl groups, and condensation reactions with acids ), Storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, coupling agent, antioxidant, thermal stabilizer, conductivity enhancer, electrification An inhibitor, a radiation blocking agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a physical property adjusting agent, etc., within a range not impairing the object and effect of the present invention It can be pressurized.

  Further, the foam stability of the silicon polymer foam and the compatibility of the foamable resin composition comprising the curing agent (A), the polymer (B), the hydrosilylation catalyst (C), and the foaming agent (D). In order to improve the surface active agent, a surfactant may be added. The type of surfactant is not particularly limited, but specific examples include alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl sodium sulfate, poly Oxyethylene alkyl ether acetate, lauryltrimethylammonium chloride, alkoxypropyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride solution, alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, Nonionic surface activity such as alkylamidopropyl betaine, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester And the like.

  Furthermore, the foamable resin composition of the present invention comprising a curing agent (A), a polymer (B), a hydrosilylation catalyst (C), and a foaming agent (D) component can have storage stability if necessary. Storage stability improvers may be added to improve. 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 such storage stability improvers include, for example, compounds containing aliphatic unsaturated bonds, organophosphorus compounds, organosulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. And at least one selected from these groups can be used. Specific examples include benzothiazole, thiazole, dimethyl malate, dimethyl acetylenedicarboxylate, 2-pentenenitrile, 2,3-dichloropropene, quinoline, and the like, and at least one selected from these groups is used. However, it is not limited to these. Among these, thiazole, benzothiazole, and dimethyl malate are particularly preferable in terms of both pot life and fast curability.

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

  Furthermore, if necessary, a bubble regulator may be added to the silicon-based polymer foam of the present invention. There are no particular limitations on the type of the air conditioner, and commonly used inorganic inorganic powders such as talc, calcium carbonate, magnesium oxide, titanium oxide, zinc oxide, carbon black, silica, polyether-modified silicone oil, etc. These silicone oil compounds and fluorine compounds can be used, and at least one selected from these groups can be used. The amount of the air bubble regulator used may be a commonly used amount. Specifically, when the total amount of the curing agent (A), polymer (B), and hydrosilylation catalyst (C) is 100 parts by weight, 0.1 to 100 parts by weight is preferable, and 0.5 to 50 is preferable. Part by weight is more preferred.

  Although the manufacturing method of the foam of this invention does not have limitation in particular, For example, it can manufacture as follows.

  A mixture of optional components such as the curing agent (A), the polymer (B), the hydrosilylation catalyst (C), the foaming agent (D), and the cell regulator is stirred and mixed to prepare a foamable resin composition. . This foamable resin composition is poured into a mold and cured to obtain a foam.

  When a liquid or solid is used as the foaming agent (D), it has at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain is composed of a saturated hydrocarbon unit or an oxyalkylene unit. A linear polymer (B) having a number average molecular weight of 10,000 or more, a hydrosilylation catalyst (C), a blowing agent (D), and a curing agent (A) having at least two hydrosilyl groups in the molecular chain, as required Accordingly, after adding and mixing other optional components, the mixture is poured into a mold and heated and cured under appropriate conditions to obtain the silicon polymer foam of the present invention.

  When a gas is used as the foaming agent (D), first, a mixed solution of optional components such as a curing agent (A), a polymer (B), a hydrosilylation catalyst (C), and a cell regulator is mixed by stirring. And a resin raw material. Next, the resin raw material and the foaming agent (D), which is a gas, are allowed to coexist in a sealed state, and are preferably compressed in the range of about 0.001 to 50 MPa, more preferably in the range of about 0.01 to 40 MPa. . Immediately, the compressed resin material is transferred to a mixer and stirred at high speed. At this time, the gas is dispersed in the resin raw material. Next, the resin raw material in which the gas is dispersed is pressurized. The silicon-based polymer foam of the present invention is obtained by placing the resin raw material obtained after pressurization into a mold by means such as press-fitting and heating. The pressurizing condition and heating condition vary depending on the expansion ratio and viscosity, and are adjusted accordingly. From the standpoint of foaming (amount of gas to be dispersed) and the maintenance of bubbles after foaming, the viscosity of the resin composition before addition of the foaming agent measured at 4 rpm using a B-type viscometer at room temperature (23 ° C.) is 100 to 3000 P, for example. (Poise) is preferable, and it is more preferable that it is 300-1500P. When the viscosity is lower than 100P, a suitable foam may not be obtained due to bubble breakage, and when it is higher than 3000P, gas dispersion failure may occur.

  The silicon polymer foam of the present invention obtained as described above has an ASKER FP hardness of preferably 50 or less. The silicon polymer foam of the present invention has such a softness.

  Although it does not specifically limit as a form of the foam at the time of shaping | molding, For example, what was shape | molded in the form of a plate shape, a sheet form, an indeterminate lump shape, a bead shape, or a bag shape or clothes, etc. are mentioned. Further, the foam may be used alone, or may be used by being integrally formed with a raw material such as an unfoamed plastic, a foam having a different expansion ratio, a film, a cloth, a nonwoven fabric, or paper.

  Furthermore, a cloth or non-woven fabric made of cotton, acrylic fiber, hair, polyester fiber or the like may be appropriately bonded to the surface of the silicon polymer 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 foam of the present invention is not particularly limited, but is a polygon such as a rectangle, square, circle, ellipse or rhombus, a strip or donut with a hollow interior, and a surface. The thing with arbitrary unevenness etc. are mentioned. Moreover, you may make a through-hole suitably in order to give air permeability. The size of the foam is not particularly limited but ^is preferably from 1cm ² ~1000cm ^2, and more preferably 50cm ² ~500cm 2.

The foam of the present invention can be used, for example, as a transportation device.
Cushion materials such as seats for automobiles, construction machinery, railway vehicles, ships, airplanes, child seats, headrests, armrests, footrests, headliners, saddles / rider cushions for motorcycles / bicycles, bed mats for custom cars, cushions for campers, etc. And skin material, skin lining material,
Core materials such as ceiling materials, handles, door trims, instrument panels, dashboards, door panels, pillars, console boxes, quarter trims, sun visors, flexible containers, front mirrors, harnesses, dust covers, etc.
Vibration-absorbing and sound-absorbing materials such as floor cushions
Cushioning materials such as helmet lining, crash pad, center pyramid,
Insulation materials such as refrigerated vehicles, cold storage vehicles, tank trucks, refrigerated container vehicles,
Insulation and sealing materials such as air conditioners and car coolers,
Air seals and waterproofing materials around the radiator, dampers, etc.
Buoyancy materials such as ships and FRP board core materials,
Safety foam in fuel tank, gasket, air filter, oil filter, various sealing materials, engine anti-vibration material, energy absorption bumper, guard soundproof material, vehicle wax sponge, etc.

Pillows, comforters, mattresses, beds, mattresses, bed mats, bed pads, cushions, cots, baby neck pillows, etc.

Furniture, chairs, chairs, cushions, sofas, sofa cushions, seat cushions, and other cushions, carpets, mats, tatami mats, comforters, toilet mats, cushion materials, skin materials, skin lining materials, packing materials, etc.

Various equipment applications such as electric and electronic equipment, air conditioners, air purifiers, filters and sound absorbing materials, thermal insulation printers, engine equipment such as construction equipment and agricultural machinery, generators, refrigerators, freezers, electronic jars, microwave ovens, etc. And thermal insulation printer cleaning roller, high ink absorber, ink cartridge filter liquid crystal, seals and cushioning materials such as electronic parts,
Robot skin, liquid-tight / air-tight seal material, soundproof flooring material, clean room wiping material, conductive cushion material, antistatic cushion material, pressure sensing material, room cooler dew condensation prevention material, etc.

Various cleaning sponge applications such as cleaning cleaner, dishwashing cleaner, body cleaning cleaner, shoe polish cleaner, car wash cleaner, etc.

For toiletries, diapers, absorbent materials such as sanitary napkins, side gathers, various liquid filters, etc.

For footwear use, shoe skin material, lining, insole, shoe rub prevention pad, various shoe pads, inner boots, slippers, slipper core, sandals, sandals insoles, etc.

Cosmetic puffs, eye color chips, etc. for cosmetic tools

As various miscellaneous goods use,
Bath products such as bath pillows, massage puffs, mouse pads, keyboard armrests, workbench mats, anti-slip cushions, stationery (pen grips, penetrating seals), desk pillows, earplugs, cotton swabs, hot pack seats, cold Packing sheets, compresses, glasses pads, underwater spectacles pads, face protectors, watch pads, headphone ear pads, earphones, ice pillow covers, folding pillows and other core materials, cushioning materials, skin materials and skin lining materials,
Double-sided tape substrate,
Adsorption media such as air fresheners and stamp stands,
Sword mountain for flower arrangement,

For clothing use,
Pad materials such as shoulders and bras, liners and insulation materials such as cold protection materials, etc.

As a sports application,
Sports protectors,
Bouldering (climbing mini rock climbing 2-3m rock) mat, beat board, cushion material for high jump, landing mat for gymnastics and exercise, cushion material such as kids mat, skin material / skin lining material,
Liners such as ski boots, snowboard boots, etc.

As a toy and playground equipment use,
Hand exerciser, healing goods, key holder, stuffed toy, mannequin body, ball, massage ball and other cushion materials and stuffing, skin material / skin lining material,
From special shapes such as ornaments and monsters, casting materials for various article shapes and model production, article shape molding materials in casting methods, model sample production materials from molds, ornament production materials , Monster special molding, moldings, etc.

As a building material application,
Insulation materials for roofs, ceilings, walls and floors, sound-absorbing materials for roofs, ceilings, walls and floors, covers for water pipes, door panels, sizing panels, core materials for metal and sizing panels, core materials for partition panels, tatami mats, Thermal insulation core material such as bran core material, bathtub, joint material, sealing material, sealant backup material, glass joint material, adhesive, system ceiling insulation panel, roof insulation waterproof material, acoustic effect room sound absorption material, freezing warehouse / airtight warehouse Air-contained heat insulating materials such as heat and cold insulation materials for tanks and pipes in plants, fence shock absorbing walls, corner cushioning materials for circuit fields, seedling / horticulture soil, hydroponic cultivation materials, clean rooms Sealing materials, foot rubber for heavy loads such as vending machines, damping materials for heavy loads, buoys, etc.

As various packaging materials,
Packing materials and cushioning materials for precision equipment,
Fruit packaging materials, fruit protection packaging materials, food packaging materials such as fresh fish trays,
Carrier cushion pad,
Shock absorbers for transportation pallets, foam for sound absorption of packaging materials, etc.

For medical and nursing use
Cell sheets for regenerative medicine, artificial skin, artificial bones, artificial cartilage, artificial organs, other biocompatible materials, chemical exudation pads, hemostatic pads, gas-liquid separation filters (indwelling needle filters), patch, medical liquid absorption devices , Masks, compression pads, surgical disposable products, electrode pads for low-frequency therapy devices, mattress prevention bedsores, posture change cushions, wheelchair cushions, wheelchair seats, shower chairs and other care products, bathing care pillows, contracture It can also be used for palm protectors, taping, cast liners, prosthetic and prosthetic liners, denture bases, other dental supplies, shock absorbing pads, hip protectors, elbow / knee protectors, and wound dressings.

Moreover, the foam of this invention can be utilized suitably especially for what touches a body, or its thing. As a specific example, for transportation equipment use,
Cushion materials such as seats for automobiles, construction machinery, railway vehicles, ships, airplanes, child seats, headrests, armrests, footrests, headliners, saddles / rider cushions for motorcycles / bicycles, bed mats for custom cars, cushions for campers, etc. And skin material, skin lining material,
Core materials such as ceiling materials, handles, door trims, instrument panels, dashboards, door panels, and skin / skin lining materials,
Cushioning material such as helmet lining,
Vehicle wax sponge etc.

Pillows, comforters, mattresses, beds, mattresses, bed mats, bed pads, cushions, cots, baby neck pillows, etc.

For furniture use, chairs, chairs, cushions, sofas, sofa cushions, seat cushions and other cushions, carpets, mats, kotatsu mattresses, cushions such as toilet mats, and skins of skin such as skin and skin lining materials,

Various cleaning sponge applications such as cleaning cleaner, dishwashing cleaner, body cleaning cleaner, shoe polish cleaner, car wash cleaner, etc.

For toiletries, diapers, absorbent materials such as sanitary napkins, side gathers, various liquid filters, etc.

For footwear use, shoe skin material, lining, insole, shoe rub prevention pad, various shoe pads, inner boots, slippers, slipper core, sandals, sandals insoles, etc.

Cosmetic puffs, eye color chips, etc. for cosmetic tools

As various miscellaneous goods use,
Bath products such as bath pillows, massage puffs, mouse pads, keyboard armrests, stationery (pen grips), desk pillows, earplugs, cotton swabs, hot pack sheets, cold pack sheets, compresses, glasses pads, underwater glasses Pads, face protectors, watch pads, headphone ear pads, earphones, ice pillow covers, core materials such as folding pillows, cushion materials, skin materials and skin lining materials,

For clothing use,
Pad materials such as shoulders and bras, liners,

As a sports application,
Sports protectors,
Bouldering (climbing mini rock climbing 2-3m rock) mat, beat board, cushion material for high jump, landing mat for gymnastics and exercise, cushion material such as kids mat, skin material / skin lining material,
Liners such as ski boots, snowboard boots, etc.

As a toy and playground equipment use,
Hand exerciser, healing goods, key holder, stuffed toy, mannequin body, ball, massage ball and other cushion materials and stuffing, skin material / skin lining material,
From special shapes such as ornaments and monsters, casting materials for various article shapes and model production, article shape molding materials in casting methods, model sample production materials from molds, ornament production materials , Monster special molding, moldings, etc.

For medical and nursing use
Cell sheets for regenerative medicine, artificial skin, artificial bone, artificial cartilage, artificial organs, other biocompatible materials, chemical liquid exudation pads, hemostatic pads, gas-liquid separation filters (indwelling needle filters), patch agents, medical liquid absorption devices , Masks, compression pads, surgical disposable products, electrode pads for low-frequency therapy devices, mattress prevention bedsores, posture change cushions, wheelchair cushions, wheelchair seats, shower chairs and other care products, bathing care pillows, contracture It can also be used for palm protectors, taping, cast liners, prosthetic and prosthetic liners, denture bases, other dental supplies, shock absorbing pads, hip protectors, elbow / knee protectors, and wound dressings.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Measurement and evaluation in Examples and Comparative Examples were performed under the following conditions and methods. In addition, unless there is particular notice, the part and% of an Example and a comparative example are a basis of weight.

<Hardness measurement method>
The hardness of the foam was evaluated by the ASKER FP type hardness tester (manufactured by Kobunshi Keiki Co., Ltd.) on the sample and the indicated value. Depending on the sample, the indicated value may decrease over time, so the value immediately after placing the hardness meter was read.

<Rebound resilience evaluation>
The impact resilience was measured according to JISK6400-3, and the impact resilience was calculated. The impact resilience was measured by a method in which a steel ball (diameter 16 ± 0.5 mm, mass 16 ± 0.5 g) was dropped on a test piece without rotating. The drop height of the steel ball was 500 ± 0.5 mm, and the height of the bounce was measured at the position of the uppermost part of the steel ball. From the obtained measurement results, the rebound resilience was calculated using the following formula (3).
R = (L−16) / 500 × 100 (3)
(Where R: rebound resilience (%), L: bounce height during measurement (mm))

<Tactile evaluation>
Evaluation of tactile sensation evaluated the tactile sensation by having 20 panelists actually touch the foam. The one with good tactile sensation when pressed or rubbed was rated as “◯”, the one with neither good nor bad △, and the one with poor tactile feeling as “X”. Here, “good tactile sensation” refers to a feeling of being wrapped while being pressed because it is soft when pressed and weakly rebounds. On the other hand, those with a poor tactile feel have a strong rebound and feel resistance.

<Compound used>
In the examples and comparative examples, the compounds shown in Table 1 were used.

（実施例１）
１００部の重合体Ｂに対して、発泡剤Ｄを７．７部、触媒Ｃを０．０３２２５部加えて十分に混合し、さらに、硬化剤Ａを１２部添加してすばやく混合した。この混合物を１００ｍｌのディスポカップに注入し、４０℃に設定したオーブンで６０分加熱硬化し、シリコン系重合体を基材樹脂とする発泡体を得た。得られた発泡体の密度は２５６ｋｇ／ｍ^３であった。また、得られた発泡体の評価結果は表１に示す。

Example 1
To 100 parts of polymer B, 7.7 parts of blowing agent D and 0.03225 parts of catalyst C were added and mixed well, and 12 parts of curing agent A was further added and mixed rapidly. This mixture was poured into a 100 ml disposable cup and cured by heating in an oven set at 40 ° C. for 60 minutes to obtain a foam using a silicon-based polymer as a base resin. The density of the obtained foam was 256 kg / m ³ . The evaluation results of the obtained foam are shown in Table 1.

(Example 2)
To 100 parts of polymer B, 3.8 parts of blowing agent D and 0.03225 parts of catalyst C were added and mixed well, and 12 parts of curing agent A was further added and mixed rapidly. This mixture was poured into a 100 ml disposable cup and cured by heating in an oven set at 40 ° C. for 60 minutes to obtain a foam using a silicon-based polymer as a base resin. The density of the obtained foam was 526 kg / m ³ . The evaluation results of the obtained foam are shown in Table 1.

（比較例１）
厚み７ｍｍのポリウレタン発泡体（商品名：Ｈｉｐ Ｐｒｏｔｅｃｔｏｒ、Ｌｙｄｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ社製）を実施例１と同様に評価し、結果を表２に示した。

(Comparative Example 1)
A polyurethane foam having a thickness of 7 mm (trade name: Hip Protector, manufactured by Lyds International) was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Comparative Example 2 Cushion Pants A polyurethane foam having a thickness of 24 mm (trade name: cushion pants, manufactured by Angel Corporation) was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

  From the above results, it was found that the foams of the examples were superior in flexibility and good in touch as compared with the comparative examples. Therefore, it has been clarified that the present invention provides a silicon polymer foam having excellent flexibility, good tactile sensation, and low toxicity.

Claims (7)

A curing agent (A) having at least two hydrosilyl groups in the molecular chain;
A linear polymer (B) having at least one alkenyl group in the molecular chain, wherein the repeating unit constituting the main chain is a saturated hydrocarbon unit or an oxyalkylene unit and having a number average molecular weight of 10,000 or more,
Hydrosilylation catalyst (C),
Foaming agent (D),
A silicon-based polymer foam obtained by curing a foamable resin composition.   The silicon-based polymer foam according to claim 1, wherein the repeating unit constituting the main chain of the polymer (B) is oxypropylene.   The silicon-based polymer foam according to claim 1 or 2, wherein the curing agent (A) / the polymer (B) (mol / mol) is 1/2 or more.   The silicon polymer foam according to any one of claims 1 to 3, wherein the polymer (B) is a linear polymer having a number average molecular weight of 15000 or more.   ASKER FP hardness is 50 or less, The silicon-type polymer foam as described in any one of Claims 1-4.   The silicon-based polymer foam according to any one of claims 1 to 5, wherein the foaming agent (D) is an active hydrogen group-containing compound.   A method for producing a silicon-based polymer foam, comprising a curing agent (A) having at least two hydrosilyl groups in a molecular chain, and having at least one alkenyl group in the molecular chain to constitute a main chain A resin composition comprising a linear polymer (B) having a number average molecular weight of 10,000 or more, the repeating unit of which is a saturated hydrocarbon unit or an oxyalkylene unit, and a hydrosilylation catalyst (C) is added to a foaming agent (D ) To obtain a foamable resin composition, which is injected into a mold and cured, and the method for producing a silicon-based polymer foam according to any one of claims 1 to 6.