JP5539671B2 - Modified silicone resin foam and bedding comprising the modified silicone resin foam - Google Patents

Description

  The present invention relates to a modified silicone resin foam having good light resistance, and a bedding such as a pillow and a mattress using the same.

  In general, soft foam is often used for bedding such as pillows and mattresses, cushions, heart materials such as cushions, and pads for clothes. Among them, in particular, those using a polyurethane foam having low resilience are attracting attention in recent years. However, light resistance may be a problem with flexible polyurethane foams. For example, even in a standard use environment when used as a bedding, that is, an environment in a bedroom where sunlight enters, yellowing or embrittlement occurs. Sometimes.

  In order to solve these problems, Patent Document 1 discloses a flexible polyurethane foam having improved light resistance by adding a specific light stabilizer. As the evaluation of light resistance, only the tensile strength is evaluated. In addition, polyurethane has a problem of using an isocyanate which is toxic.

  On the other hand, Patent Document 2 discloses a foam that uses a silicon-based polymer as a base resin and does not use an isocyanate that is a concern about toxicity. Although it is described that a light stabilizer and an antioxidant can be added, there is no description about specific effects when these are added.

JP 11-246755 A JP 2008-266867 A

  While intensively examining a foam made of a silicone-based polymer described in Patent Document 2, this foam has the advantage that yellowing or embrittlement due to light is not observed as compared with urethane. In particular, it has been found that there is a problem that the surface tackiness increases.

  In addition, for this foam, when heat curing is performed for the purpose of improving dimensional accuracy at the time of molding and improving long-term storage stability of the foam, when it is yellowed or hardened after heat curing due to the influence of additives. It turns out that problems can occur.

  An object of the present invention is to provide a modified silicone resin foam that suppresses an increase in surface adhesiveness of a foam and does not yellow after heating and is hard to be hardened.

  As a result of intensive studies to solve the above problems, the present inventors have used a hindered phenol antioxidant, a hindered amine light stabilizer as a light resistance stabilizer, and a specific ultraviolet absorber. Because the modified silicone resin foam suppresses the increase in surface adhesiveness of the foam and does not turn yellow after heat curing, it is hard to become hard, so there is no problem when used as a pillow or mattress The headline, the present invention has been completed.

That is, the present invention has the following configuration.
[1] A modified silicone resin foam comprising a hindered phenolic antioxidant, a hindered amine light stabilizer, and an ultraviolet absorber as the light resistance stabilizer (E), wherein the ultraviolet absorber is a benzoate ultraviolet ray Absorber, cyanoacrylate UV absorber, benzophenone UV absorber, triazine UV absorber, oxalic anilide UV absorber, malonic ester UV absorber, benzoxazine UV absorber, oxazolone UV absorber, A modified silicone resin foam which is at least one selected from a salicylate ultraviolet absorber and a copolymer resin type ultraviolet absorber obtained by reacting and binding a reactive ultraviolet absorber.
[2] The modified silicone resin foam according to [1], wherein the ultraviolet absorber is a triazine-based ultraviolet absorber.
[3] The modified silicone resin foam according to [1] or [2], wherein the hindered amine light stabilizer is an amino ether type.
[4] Curing agent (A) having at least two hydrosilyl groups in the molecular chain, at least one alkenyl group in the molecular chain, and a repeating unit constituting the main chain consisting of oxyalkylene units. Any one of [1] to [3], which is obtained by curing a foamable liquid resin composition comprising a coalescence (B), a hydrosilylation catalyst (C), a foaming agent (D), and a light stabilizer (E). Modified silicone resin foam.
[5] Light-resistant stabilizer (E), hindered phenol-based antioxidant, hindered amine-based light stabilizer, and ultraviolet absorber, each 0.01 parts by weight or more with respect to 100 parts by weight of polymer (B) [5] The modified silicone resin foam according to [4], wherein 5 parts by weight or less is added.
[6] The modified silicone resin foam according to any one of [1] to [5], wherein the density is 20 kg / m ³ or more and 700 kg / m ³ or less.
[7] The hardness measured with a hardness tester for tofu after heat curing at 60 ° C. for 24 hours is 5 times or less of the hardness measured with a hardness tester for tofu before heat curing [1] to [6] The modified silicone resin foam according to any one of the above.
[8] A bedding using the modified silicone resin foam according to any one of [1] to [7].
[9] The bedding according to [8], wherein the bedding is a pillow or a mattress.

  The modified silicone resin foam of the present invention is excellent in light resistance, such as suppressing an increase in surface tackiness, and is hardly yellowed and hardened even after heat curing.

  The modified silicone resin foam of the present invention has good light resistance, is not easily yellowed even after heat curing, and does not become hard, so when used as a bedding such as pillows and mattresses, A bedding with little deterioration can be provided.

  The modified silicone foam of the present invention comprises a hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a specific ultraviolet absorber as a light-resistant stabilizer. A light-resistant stabilizer has the function of absorbing light of a wavelength in the ultraviolet region and suppressing the generation of radicals, or the function of capturing radicals generated by light absorption and converting them into heat energy to make them harmless. , A compound that enhances stability to light. Further, the ultraviolet absorber is a compound having a function of suppressing generation of radicals by absorbing light having a wavelength in the ultraviolet region.

  In the present invention, hindered phenolic antioxidants and hindered amine light stabilizers include benzoate UV absorbers, cyanoacrylate UV absorbers, benzophenone UV absorbers, triazine UV absorbers, and oxalic acid anilides. From UV-absorbers, malonic acid ester-based UV absorbers, benzoxazine-based UV absorbers, oxazolone-based UV absorbers, salicylate-based UV absorbers, and copolymer resin-type UV absorbers that react and bind reactive UV absorbers By using in combination with at least one selected UV absorber, it is possible to improve the light resistance more efficiently, and it is possible to obtain a modified silicone resin foam that does not yellow after heating and is hard to harden. I found out that

  Specific examples of the hindered phenol antioxidant used in the present invention include the following.

Triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 245 (manufactured by Ciba Japan)), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX (registered trademark) 1010 (manufactured by Ciba Japan Co., Ltd.)), thiodiethylenebis [3- (3 5-Di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 1035 (manufactured by Ciba Japan), benzenepropanoic acid, 3,5-bis (1,1-dimethyl) ethyl) -4-hydroxy, C ₇ -C ₉ side chain alkyl ester (trade name: IRGANOX (R) 135 (manufactured by Ciba Japan)), 4,6-bis (dodecylthiomethyl) -o-cresol (trade name: IRGANOX (registered trademark) 1726 (manufactured by Ciba Japan)), N-phenylbenzene Reaction product of amine and 2,4,4-trimethylpentene (trade name: IRGANOX (registered trademark) 5057 (manufactured by Ciba Japan)), 2-t-butyl-6- (3-t-butyl 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer (registered trademark) GM (manufactured by Sumitomo Chemical Co., Ltd.)), 3,9-bis [2- [3- (t- (Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5 · 5] undecane (trade name: S umilizer (registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)), 2,6-di-tert-butyl-4-methylphenol (trade name: NOCRACK 200 (manufactured by Ouchi Shinsei Chemical Co., Ltd.)) 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (trade name: NOCRACK NS-6 (manufactured by Ouchi Shinsei Chemical Co., Ltd.)), 2,5-di-tert-amylhydroquinone ( Product name: NOCRACK DAH (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.).

Among them, a compound containing no sulfur atom, phosphorus atom, primary amine, or secondary amine in the molecule is preferable. Specifically, triethylene glycol-bis- [3- (3-t-butyl- 5-methyl-4hydroxyphenyl) propionate] (trade name: IRGANOX (registered trademark) 245 (manufactured by Ciba Japan)), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4- hydroxyphenyl) propionate (trade name: IRGANOX (R) (manufactured by Ciba Japan KK) 1010), benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C ₇ - C ₉ side chain alkyl ester (trade name: IRGANOX (registered trade mark) 1135 (Ciba Japan (Inc.))), 2-t-butyl -6 (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer (registered trademark) GM (manufactured by Sumitomo Chemical Co., Ltd.)), 3,9-bis [2- [3- (t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer (Registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)), 2,6-di-tert-butyl-4-methylphenol (trade name: NOCRACK 200 (manufactured by Ouchi Shinsei Chemical Co., Ltd.)), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (trade name: NOCRACK NS-6 (manufactured by Ouchi Shinsei Chemical Co., Ltd.)), 2,5-di-tert-amino Hydroquinone (trade name: NOCRAC DAH (Ouchi manufactured by Shinko Chemical Industry Co., Ltd.), and the like.

  Examples of commercially available hindered phenol antioxidants include IRGANOX (registered trademark) 245, IRGANOX (registered trademark) 1010, IRGANOX (registered trademark) 1135 (above, manufactured by Ciba Japan Co., Ltd.), Sumilizer (registered trademark) GM. Sumilizer (registered trademark) GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Nocrack 200, Nocrack NS-6, Nocrack DAH (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), etc. It is not limited to.

  Specific examples of the hindered amine light stabilizer used in the present invention include the following.

  Reaction product of decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane (trade name: TINUVIN (registered) Trademark) 123 (manufactured by Ciba Japan Co., Ltd.)), cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro 1,3,5- Amino ether type such as a reaction product of triazine and a reaction product of 2-aminoethanol (trade name: TINUVIN (registered trademark) 152 (manufactured by Ciba Japan)), N-acetyl-3-dodecyl- 1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione (trade name: Hostavin® 3058 (Claria) N-acetyl type, such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: Sanol LS765 (manufactured by Ciba Japan)), Bis (1,2,2,6,6, -pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate Trade name: TINUVIN ( (Registered trademark) 144 (manufactured by Ciba Japan Co., Ltd.)), a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (trade name: TINUVIN (registered trademark)) 622LD (manufactured by Ciba Japan Co., Ltd.)), Probandioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethy 4-piperidyl) ester (trade name: Hostavin (TM) PR-31 (manufactured by Clariant Japan (Co.))), N-alkyl type hindered amine light stabilizer such as and the like.

  The hindered amine light stabilizer used in the present invention is not particularly limited, but is preferably an amino ether type. Amino ether type hindered amine light stabilizers include decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane. Reaction product (trade name: TINUVIN (registered trademark) 123 (manufactured by Ciba Japan)), cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2, Examples include a reaction product of 4,6-trichloro 1,3,5-triazine and a reaction product of 2-aminoethanol (trade name: TINUVIN (registered trademark) 152 (manufactured by Ciba Japan)). And is preferably used. Examples of commercially available amino ether type hindered amine light stabilizers include TINUVIN 123 and 152 (manufactured by Ciba Japan Co., Ltd.).

  Examples of the UV absorber used in the present invention include benzoate UV absorbers, cyanoacrylate UV absorbers, benzophenone UV absorbers, triazine UV absorbers, oxalic anilide UV absorbers, and malonic ester UV absorbers. And at least one selected from a co-polymer resin type UV absorber in which a reactive UV absorber is reacted and combined with an agent, a benzoxazine UV absorber, an oxazolone UV absorber, a salicylate UV absorber, and a reactive UV absorber. Among them, it is preferably at least one selected from triazine-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, and malonic ester-based ultraviolet absorbers, and in particular, since yellowing and hardness increase after heat curing are small, A triazine ultraviolet absorber is most preferably used.

  Specific examples of the benzoate ultraviolet absorber include 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate (trade name: Sumisorb (registered trademark) 400 (manufactured by Sumika Chemtex Co., Ltd.), phenyl salicylate and the like. Examples of commercially available benzoate ultraviolet absorbers include Sumisorb (registered trademark) 400 (manufactured by Sumika Chemtex Co., Ltd.), SEESORB 201, and EESORB 202 (all of which are manufactured by Sipro Kasei Co., Ltd.).

  Specific examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3-diphenyl-acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl-acrylate, and the like. Examples of commercially available cyanoacrylate ultraviolet absorbers include VIOSORB 910 and VIOSORB 930 (both are manufactured by Kyodo Kagaku Co., Ltd.).

  Specific examples of the benzophenone ultraviolet absorber include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy- 4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2′dihydroxy-4-methoxy-benzophenone, 2,2′dihydroxy-4, 4′-dimethoxy-benzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone and the like. Examples of commercially available benzophenone ultraviolet absorbers include VIOSORB100, VIOSORB105, VIOSORB110, VIOSORB130 (all manufactured by Kyodo Pharmaceutical Co., Ltd.), KEMISORB13, KEMISORB111, and KEMISORB1011 (all manufactured by Chemipro Chemical Co., Ltd.).

Specific examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) -phenol, 85% 2- (4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl, and oxirane [(C ₁₀ -C ₁₆ mainly C ₁₂ -C ₁₃ alkyloxy) methyl ] Reaction product with oxirane, 15% 1-methoxy-2-propanol and the like. Examples of commercially available triazine ultraviolet absorbers include TINUVIN1577FF and TINUVIN400 (both manufactured by Ciba Japan Co., Ltd.).

  A specific example of the oxalic acid anilide ultraviolet absorber is 2-ethyl-2'-ethoxy-oxyanilide (trade name: HostavinUSV (manufactured by Clariant Japan Co., Ltd.)).

  Specific examples of the malonic acid ester UV absorber include Hostavin B-CAP, Hostavin PR-25, and Hostain PR-31 (all manufactured by Clariant Japan Co., Ltd.).

  Specific examples of the benzoxazine-based ultraviolet absorber include 2,2 ′-(1,4-phenylene) -bis-4H-3,1-benzoxazine-4-one, pionine ZA-101 (Takemoto resin ( Product)).

  As the oxazolone ultraviolet absorber, for example, compounds described in JP-A-2006-45458 can be suitably used.

  Preferred examples of the salicylate ultraviolet absorber include phenyl salicylate, 4-tert-butylphenyl salicylate, SEESORB201, and SEESORB202 (manufactured by Sipro Kasei Co., Ltd.).

  Examples of the copolymer resin type ultraviolet absorber obtained by reacting and binding a reactive ultraviolet absorber include, for example, NCI-707S-30T (Nikko Chemical Co., Ltd.), UVA-635L (BASF), New Coat UVA -204W, New Coat UVA-4512W, New Coat UVA-5080W, New Coat UVA-5080W (OHV20), Vanadylene UVA-7075W, Vanadylene UVA-7076W (OHV20) (all manufactured by Shin-Nakamura Chemical Co., Ltd.), High Stave P-UV-111, High Stave P-UV-211, High Stave P-UV-311, High Stave P-UV-411 (manufactured by Dainichi Seika Kogyo Co., Ltd.), ULS-935LH, ULS-700LH, ULS-635LH, ULS -195LH, ULS-635LH It can be suitably used Kogyo Co.).

  Although the modified silicone resin foam of the present invention has a siloxane unit as a part of the main chain or as a side chain or a cross-linked chain, the majority is composed of an organic polymer.

  Among them, it is particularly preferable to use a resin obtained by curing a mixture containing a hydrosilyl group compound, an alkenyl group compound, or a hydrosilylation catalyst, which is called an addition-type modified silicone resin. It is preferable because of excellent balance and excellent balance of physical properties as bedding such as pillows and mattresses.

  In particular, the compound having a hydrosilyl group has a curing agent (A) having at least two hydrosilyl groups in the molecular chain, and the compound having an alkenyl group has at least one alkenyl group in the molecular chain. It is preferable to use the polymer (B) in which the repeating unit constituting the oxyalkylene-based unit is used because a flexible modified silicone resin foam can be obtained.

  The compound having a hydrosilyl group is preferably a curing agent (A) having at least two hydrosilyl groups in the molecular chain (hereinafter sometimes simply referred to as a curing agent (A)). That is, the curing agent (A) acts as a curing agent for the compound having an alkenyl group, which will be described later.

  The curing agent (A) has at least 2, preferably 2 to 100, more preferably 2 to 70, and still more preferably 3 to 50 hydrosilyl groups in the molecular chain. The group reacts with the alkenyl group present in the molecular chain of the compound having an alkenyl group, which will be described later, and cures. When the number of the hydrosilyl groups is less than 2, the curing rate when the composition of the present invention is cured by a hydrosilylation reaction is slowed down, which may cause poor curing. Further, when the number of hydrosilyl groups is more than 100, the stability of the curing agent (A) and the stability of the modified silicone resin foam of the present invention are deteriorated, and a large amount of hydrosilyl groups are present after curing. It tends to remain in the modified silicone resin and may cause cracks.

In the present invention, having one hydrosilyl group means having one SiH bond. For example, in the case of SiH ₂ , it has two hydrosilyl groups. However, if the number of H bonded to one Si is one, the curability is improved and it is preferable from the viewpoint of flexibility.

  Although there is no restriction | limiting in particular about the structure of the said hardening | curing agent (A), For example, the hardening | curing agent of patent document 2 is mention | raise | lifted.

  As the compound having an alkenyl group in the present invention, a polymer (B) having at least one alkenyl group in a molecular chain and a repeating unit constituting the main chain being an oxyalkylene unit (hereinafter simply referred to as a polymer). (B) may be suitably used. 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.

  Although there is no restriction | limiting in particular about the structure of the said polymer (B), For example, the oxyalkylene type polymer of patent document 2 is mention | raise | lifted.

  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 kind can be used in any amount. For example, hydrosilylation catalyst described in Patent Document 2 can be used. The catalyst and the amount used thereof are preferably used.

  In the present invention, a modified silicone resin is used as a base resin, and the base resin is foamed by including a foaming agent (D) and foaming.

  Although it does not specifically limit as a foaming agent (D) of this invention, For example, physical foaming agents, such as a volatile liquid and gas, which are normally used for organic foams, such as a polyurethane, phenol, a polystyrene, and polyolefin, Examples thereof include a chemical foaming agent that generates gas by thermal decomposition or a chemical reaction, an active hydrogen group-containing compound that generates hydrogen by reacting with a hydrosilyl group, and these may be used in combination. Specific examples include various foaming agents described in Patent Document 2. Among these, the active hydrogen group-containing compound is preferably used because it contributes to improvement in open cell ratio and expression of physical properties such as flexibility.

  As the active hydrogen group-containing compound, primary saturated hydrocarbon alcohol, carboxylic acid or water is preferably used.

  Among these active hydrogen group-containing compounds, it is preferable to contain at least one selected from the group consisting of water, alcohol, and polyether polyol from the viewpoint of reactivity and handleability. From the viewpoint of imparting wettability, a compound in which oxygen is directly bonded to carbon or water is preferable, that is, water, ethanol, and polyethylene glycols are preferable.

  In addition, a foam regulator, a filler, a storage stabilizer, a thickener 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.

  Furthermore, if necessary, foam control such as fillers, radical inhibitors, adhesion improvers, flame retardants, polydimethylsiloxane-polyalkylene oxide surfactants or organic surfactants (polyethylene glycol alkylphenyl ether, etc.) Agent, acid or basic compound (additive for adjusting the reaction between hydrosilyl group and hydroxyl group, suppressing condensation reaction with acid and accelerating with base), storage stability improver, ozone degradation inhibitor, Thickeners, plasticizers, coupling agents, conductivity enhancers, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, physical property modifiers, etc. Further, it can be added within a range that does not impair the object and effect of the present invention.

  In addition, a surfactant can be added for the purpose of improving the foam stability and the compatibility of the curing agent (A), the polymer (B), the hydrosilylation catalyst (C), and the foaming agent (D).

  Furthermore, if necessary, a storage stability improver is added to the liquid resin composition comprising the curing agent (A), the polymer (B), and the hydrosilylation catalyst (C) in order to improve the storage stability. May be. 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. Preferred 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.

  Furthermore, if necessary, a foam regulator may be added to the modified silicone resin foam of the present invention. There are no particular limitations on the type of foam regulator, which is commonly used, for example, inorganic solid powders such as talc, calcium carbonate, magnesium oxide, titanium oxide, zinc oxide, carbon black, silica, and polyether-modified silicone oil. Examples thereof include silicone oil compounds and fluorine compounds, and at least one selected from these groups can be used.

  The content of the light resistance stabilizer (E) component is preferably 0.01 parts by weight or more and 5 parts by weight or less, and more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the polymer (B). 3 parts by weight or less is more preferable, and 0.3 part by weight or more and 1.5 parts by weight or less is particularly preferable. When each compounding quantity of a light resistance stabilizer (E) component is less than this range, practical light resistance may not be obtained. On the other hand, if the blending amount of the light-resistant stabilizer (E) component exceeds this range, the curability of the modified silicone resin foam may be reduced, and a good foam may not be obtained.

As the density of the obtained modified silicone resin foam, a material having a low density is suitably used for handling as a bedding. However, when the density is extremely low, bottoming out occurs. From this viewpoint, it is preferably 20 kg / m ³ or more and 700 kg / m ³ or less, more preferably 30 kg / m ³ or more and 700 kg / m ³ or less, and particularly preferably 50 kg / m ³ or more and 500 kg / m ³ or less.

  Heat curing may be performed for the purpose of reducing the compression set of the modified silicone resin foam. The heat curing conditions are not particularly limited, but in the modified silicone resin foam in the present invention, the heating is preferably performed at 20 ° C. or higher and 200 ° C. or lower, preferably 10 minutes or longer and 72 hours or shorter. Curing is preferable because compression set is reduced. Generally, the hardness of the obtained modified silicone resin foam may be increased by heat curing, but the modified silicone resin foam of the present invention tends to suppress an increase in hardness. Specifically, the hardness measured with a tofu hardness meter (model number: SOWB-110G, manufactured by Shiro Sangyo Co., Ltd.) after heat curing at 60 ° C. for 24 hours is preferably the hardness measured in the same manner before heat curing. Is 5 times or less, more preferably 4 times or less. In addition, as a measuring method of hardness, typically, the 40% hardness test described in JISK6400 applied to urethane or the like can be mentioned, but this is a measuring method for evaluating the hardness of the entire sample. Has been. On the other hand, the evaluation of hardness by a tofu hardness meter is said to be evaluating the vicinity of the surface of the measurement sample.

  As described above, the modified silicone resin foam of the present invention has good light resistance such as suppressing an increase in surface tackiness, does not turn yellow after heat curing, and does not become hard, so when used as bedding It can be suitably used as a bedding with little deterioration in a standard use environment. Bedding includes pillows such as so-called pillows that support the head, pillows, waist pillows, leg pillows, neck pillows, eye pillows, hip pillows, triangle pillows, mattresses such as mattresses and mattresses, comforters, mattresses, etc. Futons and so on. Among these, use as pillows and mattresses is preferable because of the effect of imparting comfort during sleep.

  When used as bedding for pillows, mattresses, etc., it can be used as it is or as a pillow, mattress, or other bedding after the skin layer formed during foam molding has been excised or cut into an appropriate shape. it can. The modified silicone resin foam obtained above may be used alone, but as long as the change in hardness due to temperature, which is a characteristic of the modified silicone resin foam, is utilized, it is an unfoamed plastic, foam. It may be used by being integrally molded with materials such as foams, films, cloths, non-woven fabrics, and papers with different magnifications, and woven fabrics made of cotton, acrylic fibers, hair, polyester fibers, etc. on the surface of the modified silicone resin foam Nonwoven fabrics may be used in combination such as pasting or stitching. By combining in this way, the tactile sensation of the modified silicone resin foam can be further improved, and the bedding can also be subjected to a sweat absorbing action by the combined fabric when sweating at high temperature and high humidity.

  The shape of the modified silicone resin foam of the present invention and the bedding such as pillows and mattresses is not particularly limited, but is a polygon such as a rectangle, a square, a circle, an ellipse, a rhombus, or a strip shape. Or a donut-shaped interior, or a surface with arbitrary irregularities. However, when it is necessary to effectively develop the air permeability, it is preferable to excise the skin layer, to provide an opening in the skin layer, or to make a through hole.

  The bedding of the present invention obtained as described above can be used safely with little deterioration in a standard bedding use environment.

  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.

<Moldability>
Formability was evaluated by ○ and × for curability and shrinkage during heat curing.
○: The foam can be removed from the mold and does not shrink.
X: The foam cannot be removed from the mold. Alternatively, the foam can be removed from the mold, but shrinks.

<Hardness measurement method>
The hardness of the modified silicone resin foam is determined by using a tofu hardness meter (model number: SOWB-110G, manufactured by Shiro Sangyo Co., Ltd.) of the modified silicone resin foam before heat curing and the modified silicone resin foam after heat curing. The hardness change was calculated by dividing the hardness after curing by the hardness before curing.

<Change in appearance after curing>
The appearance change after heat curing of the modified silicone resin foam was visually observed and evaluated in three stages of ◯, Δ, and ×.
○: No change in foam color before and after heat curing Δ: Slight discoloration is observed in the foam, but is not of concern x: Remarkably discoloration is observed in the foam by heat curing

<Light resistance evaluation>
The appearance change and the surface tackiness of the sample after irradiation for 100 hours with a 63 ° C. fade meter were evaluated in three stages of ○, Δ, and ×.

<Appearance change>
○: No change in appearance △: A slight change in appearance appears to be glossy ×: The appearance has changed completely

<Surface tackiness>
The adhesiveness of the surface was evaluated by the degree of adhesion of the resin to the glass plate after lightly touching the surface of the modified silicone resin foam.
○: Adhesive resin is not on the glass plate, and the surface is not sticky. Δ: Adhesive resin is present in a portion of 50% or less of the glass plate brought into contact with the foam surface, and is partially sticky. Resin adheres to more than 90% of the board, and is totally sticky

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

(Examples 1-5, Comparative Examples 1-4)
To 100 parts of the polymer B, the light-resistant stabilizer E is added by weight, as shown in Table 2, and 20.0 parts of a foaming aid is added and stirred, and 12.3 parts of the foaming agent D is added. Add 0.0145 parts of retarder and 0.2135 parts of Catalyst C and mix well. Further, 16.1 parts of curing agent A was added and mixed quickly. This mixture was poured into a disposable cup and cured by heating in an oven at 50 ° C. for 1 hour and further in an oven at 60 ° C. for 2 hours to obtain a modified silicone resin foam.

  Furthermore, heat curing was performed at 60 ° C. for 24 hours. Table 2 shows the evaluation results of the moldability, density, hardness change before and after curing, and light resistance of the obtained modified silicone resin foam.

  From the above results, the modified silicone resin foam of the present invention is a foam having good moldability, good light resistance, and small increase in hardness even during heat curing by adding a specific light-resistant stabilizer. You can get a body.

(Examples 6 to 10)
Pillows and mattresses were produced using the materials of Examples 1-5. As a result of using these pillows and mattresses as bedding, the standard usage environment when using them as bedding, that is, when they are used in a room with sunlight, etc. It was a good bedding in that the physical properties did not change and good sleeping comfort was obtained.

Claims (9)

A light-resistant stabilizer (E) is a modified silicone resin foam comprising a hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and an ultraviolet absorber,
Ultraviolet absorber, preparative triazine-based ultraviolet absorbers, oxalic acid anilide based ultraviolet absorber, at least one kind of modified silicone resin foam selected et or malonate type ultraviolet absorber. The modified silicone resin foam according to claim 1, wherein the ultraviolet absorber is a triazine-based ultraviolet absorber. The modified silicone resin foam according to claim 1 or 2, wherein the hindered amine light stabilizer is of an amino ether type. Curing agent (A) having at least two hydrosilyl groups in the molecular chain, polymer (B) having at least one alkenyl group in the molecular chain, and the repeating unit constituting the main chain consisting of oxyalkylene units ), A hydrosilylation catalyst (C), a foaming agent (D), and a foamable liquid resin composition comprising a light-resistant stabilizer (E), and the modified silicone according to any one of claims 1 to 3. Resin foam. A light-resistant stabilizer (E), a hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and an ultraviolet absorber, each of 0.01 parts by weight to 5 parts by weight with respect to 100 parts by weight of the polymer (B). The modified silicone resin foam according to claim 4, wherein the following is added. The modified silicone resin foam according to any one of claims 1 to 5, which has a density of 20 kg / m ³ or more and 700 kg / m ³ or less. The hardness measured with a hardness meter for tofu after heat curing at 60 ° C for 24 hours is 5 times or less of the hardness measured with a hardness meter for tofu before heat curing. The modified silicone resin foam according to one item. A bedding using the modified silicone resin foam according to any one of claims 1 to 7. The bedding according to claim 8, wherein the bedding is a pillow or a mattress.