JP2009024155A - Molded object, and impact absorber comprising the molded object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded object which is lightweight and is excellent in formability and safety; and an impact absorber using the molded object. <P>SOLUTION: The molded object comprising foamed resin particles in a base resin made of a flexible resin is suitable for use as an impact absorber in, e.g., a garment, in which the absorber is attached to an adequate position in the front, sides, or back in the waist region or in the hip part. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a molded body comprising a soft resin typified by a silicon-based resin and foamed resin particles. Furthermore, it is related with the shock absorber using this.

  As foams of high molecular compounds, thermoplastic resins such as polystyrene, polyethylene, polypropylene, and polyvinyl chloride are used as bead foams, foam sheets, and foam boards, taking advantage of their heat insulation, light weight, and buffer properties. It is used in the fields of civil engineering and construction, packaging, home appliances, and automobiles. All of these require a large-scale facility to form a molded body.

  In addition to the above foam, a polyurethane foam obtained by curing and foaming a liquid resin composition is also known. Polyurethane foams are excellent in moldability but have the disadvantage of using isocyanates which are toxic. However, for example, a soft and high-magnification polyurethane foam has a good wearing feeling and is used by being provided on clothing as a protective device (soft pad) for the purpose of preventing the impact and scratches on the body during sports. Yes. On the other hand, a hard pad is also used for the same purpose. However, although the shock absorbing performance is excellent, there are problems such as poor breathability and poor wearing feeling.

  On the other hand, as a foam excellent in moldability and safety, a compound having a carbon-carbon double bond, a compound containing on average at least 1.1 Si-H groups in one molecule, A foamable resin composition having a resin particle containing a foaming agent as an essential component has been studied (for example, Patent Document 1). However, in this technique, when the foamable resin composition is cured / foamed, it is assumed that heat generated by an addition reaction between a compound having a carbon-carbon double bond and a compound containing a Si—H group is used. Therefore, a sufficient amount of heat for foaming the resin particles containing the foaming agent cannot be obtained, and as a result, only a low-magnification foam of about 5 to 10 times is obtained.

Accordingly, there is a demand for a foam that has a high expansion ratio and preferably does not use a raw material that is toxic. The reason is that such a foam can be used as an impact absorbing pad for the purpose of preventing the occurrence of impacts and wounds on the body during sports and for preventing the femoral neck fracture of the elderly.
JP-A-7-196836

  An object of the present invention is to provide a molded article that is lightweight and has excellent moldability and safety, and an impact absorber using the molded article.

  As a result of intensive studies for solving the above problems, the present inventors have achieved excellent moldability and safety by using a soft resin typified by a silicon-based resin containing foamed resin particles. It was found that a body was obtained, and the present invention was completed.

  That is, the first of the present invention relates to a molded article comprising foamed resin particles in a base resin made of a soft resin. A preferred embodiment relates to the above-mentioned molded product, wherein the soft resin is a silicon polymer. More preferably, the silicon polymer is a curing agent (A) having at least 1.1 hydrosilyl groups on average in the molecular chain, and a compound having at least one alkenyl group on average in the molecular chain ( B), the above-mentioned molded product obtained by curing a resin composition comprising a hydrosilylation catalyst (C), more preferably at least one compound (B) in the molecular chain. The above-mentioned molded product, characterized in that the repeating unit having the alkenyl group and constituting the main chain is a polymer (b) comprising a saturated hydrocarbon unit or an oxyalkylene unit, particularly Preferably, the foamed resin particles are particles formed by foaming a thermoplastic resin and / or a thermosetting resin, and very preferably the foamed resin particles are polystyrene. Emissions, polypropylene, polyethylene, and moldings of the wherein the formed by foaming at least one resin selected from derivatives thereof, relates.

  The second of the present invention relates to the method for producing a molded article as described above, wherein the resin composition is cured after mixing the foamed resin particles with the resin composition. A third aspect of the present invention relates to an impact absorber comprising the above-described molded body. A fourth aspect of the present invention relates to a garment in which the above-described shock absorber is attached to a portion corresponding to at least one of a front body, a side part, a rear body, and a buttock around the waist.

  It is possible to provide a molded article that is lightweight and has excellent moldability and safety, and an impact absorber using the molded article.

  Hereinafter, the present invention will be described in more detail. The molded product of the present invention is a product formed by containing foamed resin particles dispersed in a soft resin as a base material. Examples of the soft resin used as a base material include thermosetting soft resins such as silicon polymers, thermosetting polyurethanes, and melamine resins, soft vinyl chloride resins, thermoplastic polyurethane resins such as polyolefins, polyolefins, and rubbers. Among them, silicon polymers are preferable from the viewpoint of safety. In addition, fillers, storage stabilizers, plasticizers, thickeners and the like may be added to the base resin as necessary to the extent that the effects of the present invention are not lost.

  The silicon polymer that can be used in the present invention is not particularly limited as long as it is a resin having a siloxane unit in the molecular skeleton. For example, a compound having a hydrosilyl group, a compound having an alkenyl group, hydrosilylation It is preferable to use a resin obtained by curing a resin composition containing a catalyst because of excellent balance of moldability, mechanical properties, and various physical properties as an impact absorber. More preferably, the compound having a hydrosilyl group is “a curing agent having an average of at least 1.1 hydrosilyl groups in the molecular chain (A)”, and the compound having an alkenyl group is “at least an average in the molecular chain. It is preferable that the main component is “compound (B) having one alkenyl group” and “hydrosilylation catalyst (C)”.

  The “curing agent (A) having at least 1.1 hydrosilyl groups on average in the molecular chain” (hereinafter sometimes simply referred to as curing agent (A)) It acts as a curing agent for “compound (B) having one alkenyl group on average” (hereinafter sometimes simply referred to as compound (B)). The curing agent (A) preferably has an average of at least 1.1 hydrosilyl groups in the molecular chain, more preferably 2 to 50, still more preferably 2 to 20, and particularly preferably 2 -15, most preferably 3-12 hydrosilyl groups, so that each hydrosilyl group reacts with the alkenyl group present in compound (B) and cures. When the number of hydrosilyl groups in the molecular chain is less than 1.1, the curing rate when the liquid resin composition of the present invention is cured by the hydrosilylation reaction is slowed, which may cause poor curing. In addition, when the number of hydrosilyl groups in the molecular chain is more than 50, the stability of the curing agent (A), that is, the stability of the resin composition is deteriorated, and a large amount of hydrosilyl groups are cured after curing. It tends to remain in the resin composition and may cause cracks.

In the present invention, having one hydrosilyl group means having one SiH bond. In the case of SiH ₂ , it has two hydrosilyl groups. The number of one is better from the viewpoint of flexibility and the curability is better. 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 or less, more preferably 20000 or less and 15000 or less in terms of number average molecular weight (Mn) from the viewpoint of moldability and the like. In consideration of reactivity and compatibility with the compound (B), 300 to 10,000 is particularly preferable.

  Although there is no restriction | limiting in particular about the structure of the above hardening | curing agents (A), For example, a hydrocarbon type hardening | curing agent and a polysiloxane type hardening | curing agent can be illustrated.

The hydrocarbon curing agent is a general formula (1):
R ¹ X _a (1)
(In the formula, X is a group containing at least one hydrosilyl group, R ¹ is a 1-4 valent hydrocarbon group having 2 to 150 carbon atoms, and a is an integer selected from 1 to 4, provided that one in X. A is an integer selected from 2 to 4)
Indicated by Specific examples of 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 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,

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 the curing agent (A) is less likely to impair the compatibility with other organic polymers, the molecular weight of the portion of X _a in the general formula (1) is 500 or less In consideration of the reactivity of the hydrosilyl group, the hydrosilyl group represented by the following chemical formula 5 is preferable.

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。

Specific examples of R ¹ made of a polymer are those obtained by polymerizing an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like as a main monomer. -4 compounds, diene compounds such as butadiene, isoprene, etc. are homopolymerized or the olefin compounds and diene compounds are copolymerized and then hydrogenated. The thing which has an individual is mentioned.

Among the hydrocarbon-based curing agents represented by the general formula (1) as described above, 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 is a compound ( B) Good compatibility with B) and good reactivity when curing a resin composition comprising a curing agent (A), a compound (B), and a hydrosilylation catalyst (C) From the viewpoint that a simple network structure can be formed. Of these, a hydrocarbon group having 5 to 12 carbon atoms in R ¹ is more preferable from the viewpoint of easy availability of raw materials, and among the groups represented by formula 5, X is a cyclic polysiloxane compound. It is more preferable that the compatibility with the compound (B) is particularly improved. A compound obtained by this combination is preferable as the hydrocarbon-based curing agent. Specific examples thereof include the compounds shown in Chemical formula 8.

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、（ｉｉｉ）の方法が、製造工程が簡便なため好適に用いることができる。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) can be preferably used because the production process is 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 chain-like 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は整数、２≦ｍ＋ｎ≦５０、２≦ｍ、０≦ｎ、Ｒはメチル基、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い。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 and n are integers, 2 ≦ m + n ≦ 50, 2 ≦ m, 0 ≦ n, R is a methyl group, a polyoxyalkylene group having a molecular weight of 100 to 10,000 or a hydrocarbon group having 2 to 20 carbon atoms, and one or more. (In the case where a plurality of R are contained, these may not be the same.)

（ｍ、ｎは整数、２≦ｍ＋ｎ≦５０、０≦ｍ、０≦ｎ、Ｒはメチル基、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い。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 and n are integers, 2 ≦ m + n ≦ 50, 0 ≦ m, 0 ≦ n, R is a methyl group, a polyoxyalkylene group having a molecular weight of 100 to 10,000, or a hydrocarbon group having 2 to 20 carbon atoms. (In the case where a plurality of R are contained, these may not be the same.)

（ｍ、ｎは整数、３≦ｍ＋ｎ≦２０、２≦ｍ≦１９、０≦ｎ≦１８、Ｒはメチル基、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い。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 and n are integers, 3 ≦ m + n ≦ 20, 2 ≦ m ≦ 19, 0 ≦ n ≦ 18, R is a methyl group, a polyoxyalkylene group having a molecular weight of 100 to 10,000, or a hydrocarbon group having 2 to 20 carbon atoms. And may contain one or more phenyl groups, and when a plurality of R are contained, these may not be the same.)

In order to improve the compatibility with the compound (B), it is preferable that R 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 compound (B) in the present invention is not particularly limited as long as it has at least one alkenyl group on average in the molecular chain, and examples thereof include compounds having a molecular weight of 100 to 100,000. Specific examples include monomers such as styrene, MMA, 1-decane, and 1,9-decadiene, polyethers having an alkenyl group at the terminal or side chain, polyesters, and polyolefins. The compound (B) is a component that is cured by a hydrosilylation reaction with the curing agent (A). Since the compound (B) has at least one alkenyl group in the molecular chain, the hydrosilylation reaction occurs to become a polymer and is cured. . The number of alkenyl groups contained in the compound (B) is at least one on average from the viewpoint of hydrosilylation reaction with the curing agent (A). However, from the viewpoint of curability and flexibility, both molecular chains are required. An alkenyl group is preferably present at the terminal. In particular, the compound (B) is a polymer (b) having at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain comprising a saturated hydrocarbon unit or an oxyalkylene unit. It is preferable that

The molecular weight of the polymer (b) is preferably about 500 to 50,000 in terms of number average molecular weight from the viewpoint of ease of handling when the repeating unit constituting the main chain is composed of a saturated hydrocarbon-based unit, more preferably 1000 to It is preferable that the material has a liquidity of about 30000 to fluidity. As used herein, the term that the repeating unit constituting the main chain consists of a saturated hydrocarbon-based unit is a concept that means a state that substantially does not contain a carbon-carbon unsaturated bond other than an aromatic ring. . Therefore, the main chain in the case where the repeating unit constituting the main chain of the polymer (b) is composed of a saturated hydrocarbon-based unit as described above,
(1) polymerizing an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene as a main monomer;
(2) A diene compound such as butadiene or isoprene is homopolymerized or the olefin compound and the diene compound are copolymerized and then hydrogenated.
Or the like.

  As the main chain in which the repeating unit is a saturated hydrocarbon-based unit, an isobutylene-based polymer can be used because 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. The hydrogenated polybutadiene polymer and the hydrogenated polyisoprene polymer are preferable.

  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, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, Vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinylmethylmethoxy Silane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane Lan, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl Examples include methyldimethoxysilane. Among the monomer components copolymerizable with isobutylene, vinylmethylmethoxysilane, divinyldimethoxysilane, allyldimethylmethoxysilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, etc. A compound other than a compound containing an alkoxysilyl group is preferable because it can be easily copolymerized.

  Also in the hydrogenated polybutadiene polymer or hydrogenated polyisoprene polymer, in addition to the monomer unit as the main component, the same monomer unit as in the case of the isobutylene polymer may be contained. Good.

  In addition, the polymer used as the polymer (b) has at least one alkenyl group in the molecular chain and the repeating unit constituting the main chain is a saturated hydrocarbon-based unit. In such a range, a small amount of monomer units, such as polyene compounds such as butadiene and isoprene, in which double bonds remain after polymerization, preferably 10% by weight or less, more preferably 5% by weight or less, and further preferably 1% by weight. You may make it contain in the range of% or less.

  As a method for introducing an alkenyl group into a main chain consisting of saturated hydrocarbon units to obtain a polymer (b), various proposed methods can be used, but the alkenyl group is introduced after the main chain is polymerized. It can be roughly divided into a method and a method of introducing an alkenyl group during 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)
(In the formula, Y is a chlorine atom, a bromine atom, a halogen atom such as iodine atom, ^{R 2} is ^-R 3 ^{-, -} R 3 -OCO- or ^-R 3 -CO- ^{(R 3} is 1 to 20 carbon atoms a divalent hydrocarbon group, preferably an alkylene group examples, a cycloalkylene group, an arylene group, a divalent organic group aralkylene group represented by like is) of 12 (R ₄ is from 1 to 10 carbon atoms A divalent group selected from the following hydrocarbon groups) is 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主鎖を構成する繰返し単位が飽和炭化水素系単位からなる重合体が製造できる。前記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２０００〜２００００で、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）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。

By reacting the organic halogen compound represented by the formula (1), a polymer in which the repeating unit constituting the main chain having an alkenyl group at the terminal, main chain or side chain is a saturated hydrocarbon-based unit can be produced. As a preferred specific example of the polymer, a linear number average molecular weight (Mn) having two alkenyl groups at both ends is 2000 to 20000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Examples thereof include polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene-based polymer having Mw / Mn of about 1.1 to 1.2.

When the repeating unit constituting the main chain of the polymer (b) is an oxyalkylene unit, a compound having two or more active hydrogen groups as a starting material for forming the main chain, for example, ethylene glycol, propylene glycol, bisphenol compound , Glycerin, trimethylolpropane, pentaerythritol, etc. are used to polymerize C ₂ -C ₄ alkylene oxide. Specific examples of the polymer (b) in which the repeating unit constituting the main chain is an oxyalkylene unit include two or more selected from the group of polyethylene oxide, polypropylene oxide, polybutylene oxide, ethylene oxide, propylene oxide, and butylene oxide. It is preferable to introduce an alkenyl group at the end of the copolymer, as in the case of introducing an alkenyl group into the main chain consisting of a saturated hydrocarbon-based unit. .

  As a preferred specific example of the polymer in which the repeating unit constituting the main chain is an oxyalkylene unit, the repeating unit of the main chain is preferably an oxypropylene unit from the viewpoint of improving the flexibility of the cured product. The molecular weight of the polymer in which the repeating unit constituting the main chain is an oxyalkylene-based unit is preferably from 500 to 50,000 in terms of the number average molecular weight (Mn), more preferably from 1000, in terms of the balance between reactivity and low hardness. 30000 is preferred.

The hydrosilylation catalyst (C) of the present invention is not particularly limited as long as it functions 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 formulae, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and m and n represent an integer of 1 or more.

Also, the platinum-hydrocarbon composite described in Ashby US Pat. Nos. 3,159,601 and 3,159,662, Lamoreau US Pat. The platinum alcoholate catalyst described in 220,972 and the chloroplatinic acid-olefin complex described in Modic US Pat. No. 3,516,946 are also useful in the present invention. obtain. 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, it is more preferable to use one or more selected from chloroplatinic acid, a platinum-olefin complex, and a platinum-vinylsiloxane complex from the viewpoint of catalytic activity and safety.

  The content ratio of the curing agent (A) and the compound (B) is preferably 0.1 to 50 moles of hydrosilyl groups in the curing agent (A) per mole of alkenyl groups in the compound (B). Mole is more preferred.

As content of a hydrosilylation catalyst (C), 10 ^<-8 > ^-10 < ^-1 > mol is preferable with respect to 1 mol of alkenyl groups of a compound (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 molded object may color.

  Although it does not specifically limit as a foamed resin particle in this invention, It is preferable that it is a particle formed by foaming a thermoplastic resin and / or a thermosetting resin. Examples of the thermoplastic resin that can be used for the expanded resin particles include polystyrene, polyolefin, acrylic resin, polyester, polyamide, thermoplastic elastomer, and polyvinyl chloride. Examples of the thermosetting resin that can be used for the foamed resin particles include polyurethane, phenol resin, epoxy resin, and silicon resin, and at least one of these can be used. Among these, at least one resin selected from polystyrene, polypropylene, and polyethylene is preferable from the viewpoints of weight reduction at a high magnification, miscibility with soft resins typified by silicone resins, fluidity, and moldability. Foamed resin particles formed by foaming are preferably used.

  The polystyrene is not particularly limited, and is a random, block or graft copolymer obtained from a styrene homopolymer obtained only from a styrene monomer, a monomer copolymerizable with a styrene monomer and styrene, or a derivative thereof. Examples thereof include polymers, modified polystyrene such as post-brominated polystyrene and rubber-reinforced polystyrene, and ABS resins. These can be used alone or in admixture of two or more.

  Examples of monomers copolymerizable with styrene include methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, and trichlorostyrene. Polyfunctional vinyl compounds such as divinylbenzene, (meth) acrylic compounds such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, diene compounds such as budadiene or the like Derivatives, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and the like. These can be used alone or in admixture of two or more.

  Polypropylene is not particularly limited, and is a propylene homopolymer obtained only from a propylene monomer, a monomer copolymerizable with propylene monomer and propylene, or a random, block or obtained from a derivative thereof. Examples thereof include a graft copolymer. These can be used alone or in admixture of two or more.

  Specific examples of monomers copolymerizable with propylene include α-olefin monomers having 2 to 8 carbon atoms such as ethylene, butene, pentene, hexene, heptene, and octene, and cyclic olefins such as norbornene monomers. Examples include olefins, vinyl alcohol esters such as vinyl acetate, (meth) acrylic acid alkyl esters having 1 to 6 carbon atoms, such as methyl methacrylate, ethyl acrylate, and hexyl acrylate, vinyl alcohol, methacrylic acid, and vinyl chloride. It is done. These may be used alone or in combination of two or more.

  Specific examples of polypropylene include ethylene-propylene random copolymer, ethylene-propylene-butene random terpolymer, polyethylene-polypropylene block copolymer, and homopolypropylene.

  The polyethylene is not particularly limited, and is a random, block or graft copolymer obtained from an ethylene homopolymer obtained only from an ethylene monomer, a monomer copolymerizable with an ethylene monomer and ethylene, or a derivative thereof. A polymer etc. are mentioned. These can be used alone or in admixture of two or more.

  Specific examples of monomers copolymerizable with ethylene include α-olefin monomers having 2 to 8 carbon atoms such as propylene, butene, pentene, hexene, heptene, octene, and cyclic olefins such as norbornene monomers. Examples include olefins, vinyl alcohol esters such as vinyl acetate, (meth) acrylic acid alkyl esters having 1 to 6 carbon atoms, such as methyl methacrylate, ethyl acrylate, and hexyl acrylate, vinyl alcohol, methacrylic acid, and vinyl chloride. It is done. These may be used alone or in combination of two or more.

  Specific examples of polyethylene include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and the like.

  The thermoplastic resin used for the foamed resin particles may be used in an uncrosslinked state, or may be used after being crosslinked with peroxide or radiation.

  The expansion ratio of the expanded resin particles in the present invention can be set within a range that does not impair the effects of the present invention, but is preferably 1.1 to 200 times, more preferably 1.5 to 150 times, and even more preferably 2 times. ~ 100 times. Moreover, it is preferable that the particle diameter of a foamed resin particle is 0.01-100 mm, More preferably, it is 0.05-50 mm.

  In addition, a surfactant is added for the purpose of improving the compatibility when using a resin composition comprising a curing agent (A), a compound (B), and a hydrosilylation catalyst (C) as a soft resin. You can also 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 sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene. Alkyl ether acetate, lauryltrimethylammonium chloride, alkoxypropyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride solution, alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethyl imidazolinium betaine, alkylamide Nonionic surface activity such as propylbetaine, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester And the like.

  If necessary, the molded product containing the foamed resin particles in the base resin made of the soft resin of the present invention may contain a storage stability improving agent in order to improve the storage stability. As the storage stability improver, a usual stabilizer known as a storage stabilizer for the curing agent (A) can be used. Preferred examples of such storage stability improvers include aliphatic sulfur compounds such as organic sulfur compounds such as benzothiazole and thiazole, dimethyl malate, dimethyl acetylenedicarboxylate, 2,3-dichloropropene, and acetylene alcohols. Examples include compounds containing a bond, nitrogen-containing compounds such as 2-pentenenitrile and quinoline, organic phosphorus compounds, tin compounds, and organic peroxides. At least one selected from these groups can be used. However, it is not limited to these. Among these, thiazole, benzothiazole, dimethyl malate, and acetylene alcohols are particularly preferable from the viewpoint of achieving both pot life and fast curability.

The amount of the storage stability improving agent used can be selected almost arbitrarily as long as it is uniformly dispersed in the curing agent (A) and the compound (B), but the SiH group 1 in the SiH group-containing compound of the curing agent (A) can be selected. It is preferably used in the range of 10 ⁻⁶ to 10 ⁻¹ mol with ^respect to mol. If the amount used is less than 10 ⁻⁶ mol, the storage stability of the curing agent (A) may not be sufficiently improved, and if it exceeds 10 ⁻¹ mol, the curability may be insufficient.

  If necessary, the molded product containing the foamed resin particles in the base resin composed of the soft resin of the present invention may further include a filler, an anti-aging agent, a radical inhibitor, an ultraviolet absorber, and an adhesive improvement. Agent, flame retardant, acid or basic compound (additive for adjusting the reaction between hydrosilyl group and hydroxyl group, suppressing condensation reaction with acid and accelerating with base), ozone degradation inhibitor, light stabilizer, Thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity enhancer, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposer, lubricant, pigment, metal inert An agent, a physical property modifier and the like can be added within a range not impairing the object and effect of the present invention.

  The shock absorber of the present invention is characterized in that a molded body containing foamed resin particles in a base resin made of a soft resin is used as the material.

<Manufacture of shock absorber using molded body>
An impact absorber is obtained as follows using a molded body containing foamed resin particles in a base resin composed of an upper soft resin.

<Manufacture of molded body>
For example, as a soft resin, a curing agent (A) having at least 1.1 hydrosilyl groups on average in a molecular chain, a compound (B) having at least one alkenyl group on average in a molecular chain, hydrosilyl In the case of using a resin obtained by curing a resin composition comprising a crystallization catalyst (C), a resin composition comprising a curing agent (A), a compound (B), and a hydrosilylation catalyst (C) is further known. From the viewpoint of moldability, a method in which the foamed resin particles obtained separately by the above technique are contained and cured is preferable. Although the said hardening method changes with compounding conditions, the method of heat-curing after mold injection is mentioned, for example.

<Manufacture of shock absorber>
The molded body obtained above can be used as an impact absorber as it is, or a skin layer formed at the time of molding can be excised or cut into an appropriate shape. However, for applications that require effective expression of air permeability, it is preferable to excise the skin layer, to provide an opening in the skin layer, or to make a through hole. Although it does not specifically limit as a form of the molded object 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 molded body may be used alone, or may be used by being integrally molded with a raw material such as an unfoamed plastic, foam, film, cloth, nonwoven fabric, or 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 molded body obtained above using an adhesive, and then used for the shock absorber. . By sticking together in this manner, the feel of the molded body can be improved, and further, the sweat absorbing action can be applied by the bonded fabric during exercise or sweating at high temperature and high humidity. The shock absorber of the present invention is used for pads and the like.

The shape of the shock absorber of the present invention is not particularly limited, but is a polygon, such as a rectangle, square, circle, ellipse, or rhombus, or a strip or donut with a hollow interior, surface And those with arbitrary irregularities. Moreover, you may make a through-hole suitably in order to give air permeability. The size of the impact absorber is not particularly limited but ^is preferably from 1cm ² ~1000cm ^2, and more preferably 50cm ² ~500cm 2.

  When the shock absorber of the present invention is used as a pad, it is preferably used by being attached to clothing. The garment to which the shock absorber is attached is not particularly limited. For example, garments that cover part or all of the lower body are preferable, such as slacks, jeans, training pants, Sabrina pants, Nikkapokka, half pants, Bottoms as outerwear to be worn on the lower body, shorts, trunks, boxer briefs, briefs and other pants, girdles, and pants etc. Innerwear, socks, tabi, tights, leg warmers, clothing to be worn on the feet such as leg ties, dresses that cover the whole body, such as dresses, dresses, joints, ties, costumes, and tights, aprons, disposable clothes, white robes, exterior Examples include protective clothing such as protectors. Among these, for the purpose of absorbing an impact at a site where fracture is likely to occur, a subon or pants, particularly pants are preferred.

  The method of attaching the shock absorber to clothing is not particularly limited, but the shock absorber will not shift due to the shearing force applied when wearing or washing, and it will improve the fit to the body and ease of exercise. In order to give, the method which sews this shock absorber to cloth | dough in a quilt shape can be illustrated. For this purpose, the shock absorber may be fixed by sewing with a thread. At this time, the shock absorber may be in contact with the body or through a cloth. Moreover, for example, a method of making a pocket and detachably attaching it in the pocket is also mentioned.

  The position where the shock absorber of the present invention is attached to the garment is preferably attached to a portion corresponding to at least one of the front body, the side part, the back body, and the buttocks in the waist.

  Also, where the subcutaneous fat, which inherently relieves shocks caused by falls, is relatively thin and the impact is strong against bones, emphasis is placed on shock absorption, pads with thick molded bodies, and the subcutaneous tissue is thick. Although there is some inherent shock absorption capability, it may be possible to use two or more types of pads in combination with one pant with emphasis on wearability on the buttocks and the like that are susceptible to impact from the buttocks or the like. In addition, the impact absorber of the present invention is used in a place where the impact is strongly received if necessary in terms of wearability and the like, and another impact absorber is placed in a place where the impact is relatively relaxed. You can use it. Examples of other impact absorbers include urethane foam, polyethylene foam, acrylic foam, nonwoven fabric, and three-dimensional fabric.

  In addition, the fabric used for clothing is not particularly limited, such as a material and a knitting method, but for example, a fabric with an uneven surface is used to improve air permeability and shock absorption. It is preferable to use a knitting structure or a pile knitting in which uneven shapes appear on the surface. In particular, it has been found that the above-described effects can be exhibited by attaching these fabrics to a place located on the body side of clothing. Furthermore, a stretch material may be used around the pad in order to reduce the impact efficiently by bringing the pad into close contact with the body.

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

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

＜衝撃吸収体の密度測定法＞
得られた成形体の重量を秤量し、型枠体積で除して密度を算出した。なお、成形不良（型枠内充填不足）のものに関しては、得られた成形体の外形を測定して得られた体積から算出した。

<Density measurement method of shock absorber>
The weight of the obtained molded body was weighed and divided by the mold volume to calculate the density. In addition, about the thing of a shaping | molding defect (insufficient filling in a formwork), it computed from the volume obtained by measuring the external shape of the obtained molded object.

Example 1
First, 25 parts of silica (trade name: Nipseal SS-50A, manufactured by Tosoh Silica Co., Ltd.) is added to 100 parts of the polymer B-1, and an antioxidant (trade name: IRGANOX 245, Ciba Specialty). 1 part of Chemicals Co., Ltd. was blended and stirred and mixed at room temperature. Separately, 200 parts of calcium carbonate (MC Coat S-20 manufactured by Maruo Calcium Co., Ltd.) and 1 part of the same antioxidant as above were blended with 100 parts of the polymer B-1, and stirred and mixed at room temperature. did. The respective mixtures were designated as a mixture B-1a and a mixture B-1b, respectively.

  950 parts of the polymer B-1, 1,000 parts of the mixture B-1a, 750 parts of the mixture B-1b, 40.33 parts of the curing agent A-1 and dimethyl maleate (Nacalai Tesque) 0.03434 parts and 0.35142 parts of 3-methyl-1-pentyn-3-ol (manufactured by Nissin Kagaku Kogyo Co., Ltd.) and 0.774 parts of catalyst C-1 respectively. A base resin material made of a silicon-based polymer was obtained by mixing parts and defoaming under reduced pressure.

A foamed resin particle-containing liquid resin composition was obtained by mixing 900 parts of expanded polypropylene resin particles (expanding ratio: 50 times) with the base resin material made of the above silicon polymer and stirring at room temperature. This liquid resin composition is poured into a rectangular mold having a thickness of 18 mm, a long side of 132 mm, and a short side of 112 mm, and is cured by heating in an oven set at a temperature of 120 ° C. for about 30 minutes. A molded body containing foamed resin particles in a base resin made of coalescence was obtained. The density of the obtained molded body was 90 kg / m ³ .

(Example 2)
To 100 parts of the polymer B-2, 0.08 part of the catalyst C-2 is added and mixed well. Furthermore, 20 parts of expanded polypropylene resin particles (expansion ratio 50 times) and 13 parts of the curing agent A-2 are added. Part was added and mixed quickly. This mixture is poured into an elliptical mold having a thickness of 20 mm, a major axis of 165 mm, and a minor axis of 115 mm, cured by heating in an oven set at 40 ° C. for 60 minutes, and expanded resin particles in a base resin composed of a silicon-based polymer. To obtain a molded body containing. The density of the obtained molded body was 150 kg / m ³ .

(Comparative Example 1)
To 100 parts of the polymer B-2, 0.08 part of the catalyst C-2 is added and mixed thoroughly, and further, 20 parts of expandable polystyrene resin particles containing 5% by weight of butane and 13 parts of the curing agent A-2. Added and mixed quickly. This mixture was poured into an elliptical mold having a thickness of 20 mm, a major axis of 165 mm, and a minor axis of 115 mm, and cured by heating in an oven set at 40 ° C. for 60 minutes. The obtained resin did not expand completely in the mold, and the density was 920 kg / m ³ .

  As described above, molding was poor in the comparative example, whereas in the example, a molded article having good moldability and light weight was obtained. That is, it has been clarified by this patent that it is possible to provide a lightweight and excellent moldability comprising foamed resin particles in a base resin made of a silicon polymer having excellent safety.

Claims (9)

  A molded product comprising foamed resin particles in a base resin made of a soft resin.   The molded body according to claim 1, wherein the soft resin is a silicon-based polymer. Silicon polymer
A curing agent (A) having at least 1.1 hydrosilyl groups on average in the molecular chain;
Compound (B) having at least one alkenyl group on average in the molecular chain,
Hydrosilylation catalyst (C),
The molded product according to claim 2, which is obtained by curing a resin composition comprising   Compound (B) is a polymer (b) having 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. The molded article according to claim 3, wherein the molded article is provided.   The molded resin according to any one of claims 1 to 4, wherein the foamed resin particles are particles formed by foaming a thermoplastic resin and / or a thermosetting resin.   The molded resin according to any one of claims 1 to 5, wherein the foamed resin particles are formed by foaming at least one resin selected from polystyrene, polypropylene, and polyethylene.   The method for producing a molded article according to any one of claims 3 to 6, wherein the resin composition is cured after mixing the foamed resin particles with the resin composition.   An impact absorber comprising the molded body according to any one of claims 1 to 6.   The clothing which attaches the impact-absorbing body of Claim 8 to the site | part corresponding to at least 1 of the front body, side part, back body, and buttocks in the waist.