JP2000302975A - Curable resin composition and expandable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition and an expandable resin composition having good workability and storage stability, capable of curing of foaming and curing under heating at normal temperature or relatively low- temperature and capable of providing a cured product or foam excellent in flame retardancy. SOLUTION: This curable resin composition comprises (A) an organic compound having a carbon-carbon double bond, (B) a compound having an SiH group, (C) aluminum hydroxide having >=2 μm and <=40 μm average particle diameter. This expandable resin composition further comprises (D) a foaming agent and/or a compound having OH group in addition to the above composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cured product having excellent storage stability and workability, which can be cured or foamed under heating at room temperature or relatively low temperature, and which has excellent flame retardancy. Provided are a curable resin composition and a foamable resin composition from which foams can be obtained.

[0002]

2. Description of the Related Art Curable compositions having flame retardancy are used in construction,
Foams having flame retardancy are widely used in the fields of electricity and automobiles, and also in the field of building materials.Halogen-based flame retardants, which are currently used as flame retardants, generate toxic gases during combustion. There is a demand for a change to safer flame retardants. The use of inorganic compounds such as aluminum hydroxide as a safer flame retardant or filler has been considered.However, in order to improve the flame retardancy with a conventional curable composition, a large amount of inorganic flame retardants must be used. It had to be added, and as a result, the viscosity became high and sufficient workability could not be obtained. In addition, when an inorganic flame retardant is added to a liquid composition having a low viscosity, there is a problem that the composition sediments over time and storage stability is poor.

In general, inorganic fillers having a small particle size are preferably used. However, when these are used, a composition having high viscosity and poor workability, but hardly sedimented is obtained. Conversely, when an inorganic filler having a large particle diameter is used, the composition becomes low in viscosity and workability is good, but the composition easily sediments. For this reason, it has been conventionally difficult to achieve both workability and storage stability (settling).

[0004]

The present invention solves the above problems and provides a curable resin composition and a foamable resin composition having good workability, storage stability, and flame retardancy. The purpose is to:

[0005]

As a result of voluntary examination, the present inventors have found that the organic compound having a carbon-carbon double bond as the component (A) and the compound having a SiH group as the component (B) are separated. In the curable resin composition, and in the foamable resin composition further comprising a foaming agent and / or a compound having an OH group as the component (D), the component (C) has an average particle diameter of 2 μm or more and 40 μm or less. It has been found that by adding aluminum hydroxide having a specific particle size, the flame retardancy is significantly improved without lowering workability and storage stability.

That is, the curable resin composition of the present invention comprises:
(A) an organic compound having a carbon-carbon double bond, and (B) a compound having a SiH group, and (C) aluminum hydroxide having an average particle diameter of 2 μm to 40 μm. is there.

Further, the foamable resin composition of the present invention comprises:
(A) an organic compound having a carbon-carbon double bond, (B)
Compound having SiH group, (D) blowing agent and / or OH
(C) having an average particle diameter of 2
It contains aluminum hydroxide of not less than μm and not more than 40 μm.

The component (A) in the curable resin composition and the foamable resin composition includes a phenol compound, a bisphenol compound and a polyether compound having one or more carbon-carbon double bonds in one molecule. Organic compounds selected from coalesced and polyester polymers can be used.

As the component (B), a chain and / or cyclic organosiloxane having one or more SiH groups in one molecule can be used, and one or more SiH groups in one molecule can be used.
A chain having an H group and having in its molecule a skeleton introduced from one or more compounds selected from styrene derivatives, phenol derivatives, bisphenol derivatives, polyether derivatives, polyester derivatives, and olefin derivatives; And / or cyclic organosiloxane can be suitably used.

The foaming agent of the component (D) has a boiling point of 100
Volatile compounds below ℃ can be used. Also, O
As the compound having an H group, an organic compound in which an OH group is directly bonded to a carbon atom and / or water can be used.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, (A) to (C) used in the curable resin composition and / or foamable resin composition of the present invention.
Each component of (D) will be described in order. (A) Component First, an organic compound having a carbon-carbon double bond, which is the (A) component, will be described.

The skeleton structure of component (A) is not particularly limited as long as it satisfies the condition that it does not substantially contain a siloxane bond. Examples of the monomer skeleton include phenolic, bisphenolic, epoxy resin monomers, and isocyanate. Nart or a mixture thereof. Polymers include polyether, polyester, polycarbonate, saturated hydrocarbon, polyacrylate, polyamide, diallyl phthalate, phenol-formaldehyde (phenol resin), polyurethane, polyurea, and melamine. Examples thereof include a skeleton of a polymer and an epoxy resin, and more preferably a phenol compound, a bisphenol compound, a polyether polymer, and a polyester polymer in terms of availability. Specific examples of the phenolic and / or bisphenolic compound include a compound represented by the following general formula (1).

[0013]

Embedded image (However, in the formula (1), R ^1, R ² represents a hydrogen atom or a methyl ^{group, R 3, R 4, R} 5 represents a divalent substituent of 0-6 carbon atoms, R ⁶ , R ⁷ and R ^{8 each} represent a monovalent substituent having 0 to 6 carbon atoms, and X ¹ and X ^{2 each} represent a divalent substituent having 0 to 10 carbon atoms. Represents an integer of 0 to 300, s represents an integer of 1 to 300, p, q, r represent 0
Represents an integer of 1 to 3. Examples of the bisphenol compound include O, O'-diallylbisphenol A, 2,2'-diallylbisphenol A, a reaction product of bisphenol A with allyl glycidyl ether or glycidyl methacrylate, bisallyl carbonate of bisphenol A, bis (Meth) acrylates and the like.

In addition, isocyanate compounds such as 4,4'-methylenebis (phenylisocyanate) and tolylene-2,6-diisocyanate, allyl alcohol,
Urethane and urea compounds obtained by reaction with allyl glycol or allylamine can also be used.

Further, an allyl ether compound obtained by Michael addition of allyl alcohol, allyl glycol or the like to bis (meth) acrylic acid ester can also be used.

Specific examples of polyether polymers include allyl-terminated polypropylene oxide and polyethylene oxide. Specific examples of the polyester polymer include an allyl ester of a phthalic anhydride-ethylene glycol polymer or a phthalic anhydride-diethylene glycol polymer.

The carbon-carbon double bond of the component (A) is
There is no particular limitation as long as the addition reaction by the hydrosilylation with the component (B) is possible, as long as it is bonded to the skeleton portion of the component (A) through a divalent or higher substituent.

The divalent or higher valent substituent is preferably a substituent having 0 to 10 carbon atoms containing only one or more of C, H, N, O, S and halogen as constituent elements. It is not limited, and two or more of these divalent or more substituents may be connected by a covalent bond to form one divalent or more substituent.

Among the carbon-carbon double bonds, vinyl, allyl, methallyl, allyloxy, acryl and methacryl groups are preferred from the viewpoint of availability of raw materials and ease of synthesis.

The carbon-carbon double bond may be present anywhere in the molecule, but is preferably present on the side chain or terminal from the viewpoint of reactivity. The number is 1 in terms of curability.
The average is preferably more than one per molecule, more preferably two or more. However, if molecules having two or more carbon-carbon double bonds are included to some extent, curing may be sufficient even if the average value is two or less.

The structure of the component (A) may be linear or branched, and the molecular weight is not particularly limited.
Any one of about 000 can be suitably used, and 100
Particularly preferred are those of ~ 20,000.

As the component (A), one type may be used alone, or two or more types may be used in combination. Component (B) Next, the compound having a hydrosilyl group as the component (B) will be described.

The compound having a hydrosilyl group that can be used in the present invention is not particularly limited.
No. 96/15194 can be used, but from the viewpoint of availability, a chain and / or cyclic polyorganosiloxane having one or more hydrosilyl groups in one molecule can be suitably used. .

In particular, one molecule has one or more hydrosilyl groups, and is introduced from one or more compounds selected from styrene derivatives, phenol derivatives, bisphenol derivatives, polyether derivatives, polyester derivatives, and olefin derivatives. It is preferably a chain and / or cyclic polyorganosiloxane having a skeleton in its molecule.

Specific examples of the linear or cyclic organohydrogenpolysiloxane include compounds represented by the following general formula (2) or (3).

[0026]

Embedded image (In the equation (2), m ≧ 2, n, l ≧ 0, p ≧ 1, 3
≦ (m + n + 1) × p ≦ 80, and R ⁹ , R ¹⁰ , R ¹² , R
¹³ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms,
It may contain one or more aromatic substituents.
R ¹¹ substantially represents a polyoxyalkylene group. )

[0027]

Embedded image (In the equation (3), m ≧ 2, n, l ≧ 0, p ≧ 1, 3
≦ (m + n + 1) × p ≦ 20, and R ⁹ , R ¹⁰ , R
¹¹ is the same as above. Further, those in which two or more of the above-described chain or cyclic organohydrogenpolysiloxanes are present in one molecule via a divalent or higher valent substituent are also preferably used. Compounds represented by the general formulas (4), (5) and (6) are exemplified.

[0028]

Embedded image

[0029]

Embedded image (In equations (4) and (5), m ≧ 2, n, l ≧ 0,
p ≧ 1, 3 ≦ (m + n + 1) × p ≦ 80, and R ⁹ , R
¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same as above. R ¹⁴ represents a divalent or higher valent substituent. )

[0030]

Embedded image (In the equation (6), m ≧ 2, n, l ≧ 0, p ≧ 1, 3
≦ (m + n + 1) × p ≦ 20, and R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹⁴ is the same as above. In the formulas (4) to (6), the divalent or higher substituent represented by R ¹⁴ is not particularly limited, and may be a carbon-carbon double bond such as a vinyl group, an allyl group, an acryl group, and a methacryl group; OH groups such as hydroxyl group and carboxyl group in the molecule
A compound derived from a compound having at least one compound is appropriately used.

The compounds represented by the above formulas (4) to (6) are merely examples, and for example, the hydrosilyl group in each compound is further linked to a chain or cyclic organohydrogen through another substituent. It is of course possible to use a structure having a structure bonded to polysiloxane.

As the compounds represented by the above general formulas (2) and (3), the compounds represented by the following general formulas (7) and (8) are particularly preferably used.

[0033]

Embedded image (In the equation (7), m ≧ 2, n ≧ 0, l, k, q ≧ 1,
p is an integer of 0 to 5, 10 ≦ (m + n + 1 + k) × q ≦ 8
0, and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same as above. )

[0034]

Embedded image (In the equation (8), m ≧ 2, n ≧ 0, l, k, q ≧ 1,
p is an integer from 0 to 5, 3 ≦ (m + n + 1 + k) × p ≦ 20
And R ⁹ , R ¹⁰ and R ¹¹ are the same as above. As a method for obtaining the compounds obtained by the above general formulas (2) and (3), polyoxyalkylene having a functional group capable of reacting with a hydrosilyl group such as a double bond (for example, an allyl group) or an OH group at the terminal A compound and an aromatic ring-containing organic group,
A method of reacting with a polyorganohydrogensiloxane, a method of synthesizing a polyorganohydrogensiloxane using a silicon compound having a polyoxyalkylene chain and an aromatic ring-containing organic group in advance, or a method of synthesizing the above silicon compound with a polyorganosiloxane Can be used.

Specifically, for example, the following equations (9) and (10):

[0036]

Embedded image (In the equation (9), m ≧ 2, n ≧ 0, p ≧ 1, 10 ≦ (m +
n) × p ≦ 80, and R ⁹ , R ¹⁰ , R ¹² and R ¹³ are the same as above. ),

[0037]

Embedded image (In the formula (10), m ≧ 2, n ≧ 0, p ≧ 1, 3 ≦ (m +
n) × p ≦ 20, and R ⁹ and R ¹⁰ are the same as above. )
In represented by a chain, and cyclic _{polyorganohydrogensiloxane, H 2 C = CHCH 2 -} [(PO) n- (EO) m] l-OH H 2 C = CHCH 2 - [(PO) n- (EO) m] l-OC
_{H 3 H 2 C = CHCH 2} - [(PO) n- (EO) m] l-OC 2
_{H 5 H 2 C = CHCH 2} - [(PO) n- (EO) m] l-OC 3
_{H 7 H 2 C = CHCH 2} - [(PO) n- (EO) m] l-OC 4
_{H 9 H 2 C = CHCH 2} - [(PO) n- (EO) m] l-OP
h HO - [(PO) n- (EO) m] l-CH 3 HO - [(PO) n- (EO) m] l-C 2 H 5 HO - [(PO) n- (EO) m] _{l-C 3 H 7 HO -} [(PO) n- (EO) m] l-C 4 H 9 HO - in [(PO) n- (EO) m] l-Ph ( above formulas, 1 ≦ ( m + n) × l ≦ 80, m,
n ≧ 0, l ≧ 1) and the like, and styrene, 4-methylstyrene, 2,4-methylstyrene,
α-methylstyrene, 4-bromostyrene, 2-vinylnaphthalene, allylbenzene, allylanisole, allylphenylether, o-allylphenol, p-isopropenylphenol, phenol, o-cresol,
The reaction includes a reaction with an aromatic ring-containing compound such as benzyl alcohol, phenethyl alcohol, benzoic acid, and 4-hydroxybenzoic acid.

Specific examples of the linear polyorganohydrogensiloxane represented by the formula (9) include polymethylhydrogensiloxane, polyethylhydrogensiloxane, polyphenylhydrogensiloxane, and methylhydrogensiloxane. Examples include a dimethylsiloxane copolymer, a methylhydrogensiloxane-diethylsiloxane copolymer, a methylhydrogensiloxane-methylphenylsiloxane copolymer, and an ethylhydrogensiloxane-dimethylsiloxane copolymer.

Specific examples of the siloxane unit in the cyclic polyorganohydrogensiloxane represented by the formula (10) include methyl hydrogen siloxane, ethyl hydrogen siloxane, phenyl hydrogen siloxane, dimethyl siloxane, and diethyl siloxane. Examples thereof include siloxane and methylphenylsiloxane, and those obtained by copolymerizing to form a cyclic body are used.

Here, in the polysiloxanes represented by the formulas (2) and (3), the ratio of the total silicon atoms to which the polyoxyalkylene groups and the aromatic ring-containing organic groups are bonded to all the siloxane units is referred to as a modification ratio. To

In order to obtain sufficient foam controllability, the above modification rate is generally 5 to 5 depending on the composition and mixing ratio of other components.
90% is preferred, and 5-25% is particularly preferred. However, since the denaturation rate has a distribution, the numerical values given here are average values. If the modification rate is lower than 5%, the compatibility with the organic compound having a carbon-carbon double bond is deteriorated, the foam-regulating property is reduced, and the cells of the foam do not become fine. In some cases, bubbles are generated, and a sufficient expansion ratio cannot be obtained. Conversely, when the modification ratio is higher than 90%, the hydrosilyl group equivalent becomes large, and in order to obtain a foam using this compound alone as a curing agent, a large amount is required, and only a foam having a low expansion ratio can be obtained. It is not preferable.

The ratio of the aromatic ring-containing organic groups in the above modification ratio can be arbitrarily adjusted within a range that does not adversely affect the compatibility of the mixture during the production of the foam.

The structure of the polyoxyalkylene chain is as follows:
It is preferable that the ratio of oxyethylene units is large, and the ratio of oxyethylene units to all oxyalkylene units is 50 to 100% in terms of several units. If the ratio of the oxyalkylene units is smaller than this, sufficient foam control properties cannot be obtained.

The molecular weight of the oxyalkylene chain is not particularly limited, but is preferably from 100 to 3000, more preferably from 200 to 1,000 in number average molecular weight. If the number average molecular weight is less than 100, sufficient foam control properties cannot be obtained.
If it is larger than 00, the density of the hydrosilyl group decreases, so that it is necessary to use a large amount to sufficiently cure the foam when producing the foam, and therefore, it is not preferable because only a foam having a low expansion ratio can be obtained.

As the component (B), the following (a) is used for the purpose of obtaining a foam having uniform cells, no internal cracks and voids, and suppressed shrinkage and the like generated after the completion of foaming. ), A component (b) and a compound obtained by reacting the component (c), and a compound in which a hydrosilyl group derived from the component (a) substantially remains can also be used; (a) silicon in one molecule A chain and / or cyclic organohydrogensiloxane having 3 to 10 atoms, (b) a compound having two or more functional groups capable of reacting with the hydrosilyl group of the component (a) in one molecule, c) (a)
An organic compound containing one functional group per molecule that can react with the hydrosilyl group of the component.

When a compound obtained by reacting the components (a), (b) and (c) is used as the component (B), the compatibility and foam-regulating properties are good and the foaming is completed. The effect is obtained that the subsequent shrinkage is greatly suppressed to a low shrinkage ratio of 10% or less. This is presumably because component (b) contributes to the improvement of compatibility and suppression of shrinkage, and component (c) contributes to the improvement of compatibility and foam control.

Specific examples of the chain organohydrogensiloxane of the component (a) include those represented by the following general formula (11).

[0048]

Embedded image (Where j ≧ 2, k ≧ 0, q ≧ 1, 3 ≦ (j +
k) × q ≦ 8, and R ⁹ , R ¹² and R ¹³ are the same as above. In addition, specific examples of the cyclic organohydrogensiloxane include those represented by the following general formula (12).

[0049]

Embedded image (Where j ≧ 2, k ≧ 0, q ≧ 1, 3 ≦ (j +
k) × q ≦ 10, and R ⁹ is the same as above. The number of hydrosilyl groups per molecule of the chain and cyclic siloxanes as component (a) is preferably 2 or more and 10 or less, more preferably 2 or more and 6 or less. When the number of hydrosilyl groups per molecule is less than 2, the physical strength of the finally obtained foam decreases,
As a result, shrinkage becomes difficult to be suppressed. Conversely, when the number exceeds 10, shrinkage as well as cracks may occur in the foam.

Specific examples of the component (a) include polymethyl hydrogen siloxane, polyethyl hydrogen siloxane, polyphenyl hydrogen siloxane and the like, and copolymers or mixtures thereof.

Further, more specific examples of the cyclic siloxane include 1,3,5-trimethylcyclotrisiloxane,
1,3,5,7-tetramethylcyclotetrasiloxane,
1,3,5,7,9-pentamethylcyclopentasiloxane, and mixtures thereof, and the like.

Next, regarding the component (b), examples of the functional group capable of reacting with the hydrosilyl group include a carbon-carbon double bond such as a vinyl group, an allyl group, an acryl group and a methacryl group, a hydroxyl group and a carboxyl group. Examples thereof include compounds having an OH group such as a group, and two or more of these may be present in one molecule.

The above functional group may be present anywhere in the molecule, but is preferably present on the side chain or terminal from the viewpoint of reactivity. The number of functional groups that can react with a hydrosilyl group in one molecule is preferably 2 or more and 4 or less, and 2 or more and 3 or less.
The number is more preferable. If the number of functional groups capable of reacting with the hydrosilyl group in one molecule exceeds 4, the gelling may occur during the reaction between the component (a) and the component (b), which is not preferable.

The skeleton of the component (b) is not particularly limited, and examples thereof include ordinary organic monomer skeletons or organic polymer skeletons, and inorganic compounds such as water.

Examples of the organic monomer skeleton include hydrocarbons, aromatic hydrocarbons, phenols, bisphenols, epoxy resin monomers, isocyanates, and mixtures thereof. Organic polymers include polyether, polyester, polycarbonate, saturated hydrocarbon, polyacrylate, polyamide, diallyl phthalate, phenol-formaldehyde (phenol resin), polyurethane, polyurea, and melamine. And a skeleton of an epoxy polymer or the like.

Specific examples of the component (b) include 1,9
Α, ω-alkadienes such as decadiene, divinylbenzene, diallylbenzene, 1,4-butanediol and allyl ether, phthalic anhydride and its allyl ester, O, O′-diallylbisphenol A, 2,2′-diallylbisphenol A, ethylene glycol or diethylene glycol and their allyl ethers, allyl-terminated polypropylene oxide and polyethylene oxide, phthalic anhydride-ethylene glycol polymer or allyl ester of phthalic anhydride-diethylene glycol polymer, 9-decen-1-ol, ethylene glycol Monoallyl ether and the like. In addition to these, those listed as specific examples of the component (A) can be appropriately used. In the case where the component (b) and the component (A) have a similar structure, the compatibility of the system can be increased, and a foam having fine cells can be obtained.

Although the molecular weight of the component (b) is not particularly limited, those having a molecular weight of about 100,000 or less can be appropriately used.
Those having a molecular weight of not more than 000 are preferred.

Next, regarding the component (c), the component (c)
Examples of the functional group capable of reacting with the hydrosilyl group include the same functional groups capable of reacting with the hydrosilyl group of the component (b) described above. Like the component (b), it may be located anywhere in the molecule, but is preferably located on the side chain or terminal from the viewpoint of reactivity. further,
Examples of the skeleton of the component (c) include the organic monomers and / or organic polymers listed as the skeleton of the component (b).

Specific examples of the component (c) include α-olefins such as 1-hexene, 1-octene and 1-decene, and alcohols such as 1-propanol, 1-octanol and ethylene glycol monoethyl ether. , 2
-Carboxylic acids such as ethylhexanoic acid, (meth) acryls such as butyl acrylate and methyl methacrylate,
Styrene, 4-methylstyrene, 2,4-dimethylstyrene, α-methylstyrene, 4-bromostyrene, 2-
Vinylnaphthalene, allylbenzene, allylanisole, allylphenylether, o-allylphenol,
aromatic compounds such as p-isopropenylphenol,
Examples include polyoxyalkylenes, polyesters, acrylic polymers, and the like, in which one end is substituted with an allyl group, a hydroxyl group, a (meth) acrylic group, a carboxyl group, and the other end is substituted with an organic group that does not react with the hydrosilyl group.

The molecular weight of component (c) is not particularly limited, but those having a molecular weight of about 100,000 or less can be used as appropriate.
Those having a molecular weight of not more than 000 are preferred.

The mixing ratio of the above components (a), (b) and (c), ie, the molar number of the hydrosilyl group of the component (a) is x, and the functional group capable of reacting with the component (a) of the component (b). The value of y / x and z / x is not particularly limited when the number of moles of y is y and the number of moles of a functional group capable of reacting with the component (a) of the component (c) is z. ≦ y / x ≦ 0.5, 0.
001 ≦ z / x ≦ 0.8, preferably 0.1
It is more preferable that ≦ y / x ≦ 0.4 and 0.01 ≦ z / x ≦ 0.4.

If y / x is less than 0.01, the object of the present invention is not to sufficiently suppress the shrinkage, etc.
Exceeding the range is not preferred because, during the reaction between the component (a) and the component (b), an increase in viscosity due to an increase in the molecular weight or the like occurs. When z / x is less than 0.001, the compatibility of the system is not sufficient, and as a result, the cells of the foam tend to be rough, and when it exceeds 0.8, shrinkage is suppressed. The effect tends to be reduced.

The component (a) is replaced by the components (b) and (c)
In order to cause each of the components to react with each other, a reaction (hydrosilylation) between the components (A) and (B) described below, and (B)
In general, the same type of catalyst is used when the component is reacted with the compound having the OH group of the component (D).

The compound obtained by the reaction of each of the above components (a), (b) and (c) is a mixture of compounds having various structures because the component (b) is polyfunctional. Examples include those containing a compound represented by the following formula (13). These mixtures can be used as they are without purification.

[0065]

Embedded image (In the formula (13), n represents an integer of 1 or more and 100 or less, preferably 40 or less.) As the component (B) in the present invention, one type may be used alone, or two or more types may be mixed. You may use it.

The number of hydrosilyl groups of the component (B) is
As in the case of the carbon-carbon double bond of the component (A), it is preferable that the average number per molecule be more than one, from the viewpoint of curability.
More preferably, the number is two or more. This (B)
Since the component and the component (D) undergo dehydrocondensation and participate in foaming, the number of hydrosilyl groups is determined by the desired foaming ratio, but is generally more preferably 3 or more. However, if molecules having two or more hydrosilyl groups are contained to some extent, even if the average value is two or less, curing may be sufficient. On the other hand, the upper limit of the number is preferably 80 or less, more preferably 50 or less, in view of the availability of the compound and the balance between foaming and curing.

In the foamable resin composition of the present invention, (B)
The mixing ratio of the component and the component (A) is not particularly limited, but when the number of moles of the double bond of the component (A) is X and the number of moles of the hydrosilyl group of the component (B) is Y, X: Y = 3
The range of 0: 1 to 1:30 is preferable, and 1 is more preferable.
0: 1 to 1:10, more preferably 5: 1 to 1: 5. (C) Component In the present invention, aluminum hydroxide having an average particle diameter of 2 μm or more and 40 μm or less is used as the component (C). When aluminum hydroxide (C) having an average particle diameter of 2 μm or more and 40 μm or less is used, the flame retardancy can be reduced without lowering the workability and storage stability of the curable resin composition and the foamable resin composition of the present invention. Can be improved.
In the present invention, it is particularly preferable to use aluminum hydroxide having only this specific average particle size.

This aluminum hydroxide refers to Al (O
H) ₃ or a white powder crystal represented by the chemical formula of Al ₂ O ₃ .3H ₂ O, which is generally produced by a Bayer method using bauxite as a raw material.

Although aluminum hydroxide is a product having various average particle diameters by classification, the aluminum hydroxide used in the present invention has an average particle diameter of 2 μm to 40 μm.
It is important that: The value of the average particle size of the aluminum hydroxide of the present invention is measured by a sedimentation balance method (a method of measuring the sedimentation speed of powder particles in a stationary fluid to obtain a particle size distribution. The sedimentation speed is measured using a balance. Analysis by measuring the change in total particle concentration).

The average particle size of the aluminum hydroxide used in the present invention is preferably 2 μm or more and 40 μm or less, more preferably 2 μm or less.
m to 20 μm, more preferably 2 μm to 10 μm
m or less is particularly preferred. When the average particle size is less than 2 μm, the viscosity of the composition is high and workability may not be sufficient. When the average particle size is more than 40 μm, the viscosity becomes low and the workability is good but sedimentation occurs. In some cases, the composition is easy to work with and has poor storage stability.

The amount of the component (C) added is preferably 1 to 200 parts, more preferably 2 to 100 parts, based on 100 parts (parts by weight, hereinafter the same) of the total of the components (A) and (B). Particularly preferred is 5 to 50 parts. If the amount is less than 1 part, the flame retardancy may not be sufficient, and if it is more than 200 parts, the workability and storage stability may be reduced. The component (C) can be used alone or in combination of two or more. (D) Component Next, the foaming agent and the compound having an OH group of the component (D) will be described.

First, regarding the foaming agent, as the foaming agent, those usually used for organic foams such as polyurethane, phenol, polystyrene and polyolefin can be appropriately selected and used.

The type of the foaming agent is not particularly limited.
From the viewpoint of workability and safety, it is preferable to use a compound selected from hydrocarbons, ketone compounds, organic compounds such as chlorofluorocarbons and ethers alone or in combination of two or more.

Examples of hydrocarbons include methane, ethane,
Propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclopentane, cyclobutane, cyclobutane Pentane, cyclohexane and the like.

Examples of ketone compounds include acetone,
Examples include methyl ethyl ketone and methyl isopropyl ketone.

Examples of fluorocarbons include trichlorofluoromethane (R11) and dichlorodifluoromethane (R1
2), chlorotrifluoromethane (R13), bromotrifluoromethane (R13B1), tetrafluoromethane (R14), dichlorofluoromethane (R21), chlorodifluoromethane (R22), trifluoromethane (R23), difluoromethane (R32), Fluoromethane (R41), tetrachlorodifluoroethane (R1
12), trichlorotrifluoroethane (R113),
Dichlorotetrafluoroethane (R114), dibromotetrafluoroethane (R114B2), chloropentafluoroethane (R115), hexafluoroethane (R116), chlorotrifluoroethane (R12
3), tetrafluoroethane (R134a), dichlorofluoroethane (R141b), chlorodifluoroethane (R142b), difluoroethane (R152a), octafluoropropane (R218), dichloropentafluoropropane (R225), hexafluoropropane (R236ea), penta Fluoropropane (R245
fa), octafluorocyclobutane (RC318),
Hexafluorobutane (R356mffm), pentafluorobutane (R365mfc), decafluoropentane (R4310mee) and the like can be mentioned.

In consideration of environmental issues and the like, hydrochlorofluorocarbon (HCFC), a so-called alternative fluorocarbon, is preferable to chlorofluorocarbon (CFC), and it is particularly preferable to use hydrofluorocarbon (HFC). That is, tetrafluoroethane, difluoroethane, octafluoropropane, hexafluoropropane, pentafluoropropane, octafluorocyclobutane, hexafluorobutane, and pentafluorobutane are particularly excellent.

As ethers, 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, methyl pentafluoroethyl ether, 2,2,2-trifluoroethyl ether, methyl (trifluoromethyl) tetrafluoroethyl ether, methyl-n-nonafluorobutyl ether and ethyl-n-nonafluorobutyl ether; No.

The boiling point of the blowing agent is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and particularly preferably 50 ° C. or lower. When the boiling point exceeds 100 ° C., the balance between foaming and curing is deteriorated, and a foam having a high expansion ratio cannot be obtained.

As the foaming agent satisfying the above conditions,
Although it depends on the structure of the component (A), examples thereof include hydrocarbons and fluorocarbons, and among these, C 2 or C 3 having a solubility of 5 parts by weight or more at 23 ° C. with respect to 100 parts by weight of the component (A). Hydrofluorocarbon (HF
C), C1-C3 hydrochlorofluorocarbon (HCFC), C3-C6 hydrocarbon, C3-C3
One or more selected from ketone compounds having 5 and ethers having 2 to 6 carbon atoms are preferably used.

As a specific example of these, HFC13
4a, HFC152a, HCFC141b, HCFC1
42b, HFC245fa, propane, cyclopentane, dimethyl ether, diethyl ether, methyl-n
-Nonafluorobutyl ether, ethyl-n-nonafluorobutyl ether and the like.

Next, a compound having an OH group, which is another component of the component (D), will be described.

The type of the compound having an OH group used in the present invention is not particularly limited, but a compound in which the OH group is directly bonded to a carbon atom is preferably used, and examples thereof include alcohols and carboxylic acids. Can be

Examples of alcohols include n-propanol, iso-propanol, n-butanol, iso-
Butanol, ethylene glycol and the like. Examples of the carboxylic acid include hexanoic acid, 2-ethylhexanoic acid, adipic acid, meso-1,2,3,4-tetracarboxylic acid, benzoic acid, phthalic acid, and isophthalic acid. And terephthalic acid.

For adjusting the foaming speed, two or more types of OH
Compounds can be used in combination. In this case, for example, a combination of a primary alcohol such as n-propanol and a secondary alcohol such as iso-propanol, a carboxylic acid and a primary alcohol, or a combination of a carboxylic acid and water is preferable.

The above-mentioned foaming agent and the compound having an OH group may be used alone or in combination.

In the foamable resin composition of the present invention, for foaming, for example, NaHCO ₃ , (NH ₄ ) ₂ CO ₃ , N
Inorganic blowing agents such as H ₄ HCO ₃ , NH ₂ NO ₂ , Ca (N ₃ ) ₂ and NaBH ₄ , azodicarbonamide, azobisisobutyronitrile, barium azodicarboxylate,
Organic foaming agents such as dinitrosopentamethylenetetramine and paratoluenesulfonyl hydrazide, generation of carbon dioxide by the reaction of an isocyanate with an active hydrogen group-containing compound, mechanical stirring, and the like can also be used in combination. A generally used flame retardant other than the component (C) can be added to the curable resin composition and the foamable resin composition of the present invention as long as the object and effects of the present invention are not impaired. Specifically, halogen-based agents such as tetrabromobisphenol A, tetrabromobisphenol A epoxy, and decabromodiphenyl oxide, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, tris (chloroethyl) phosphate, and tris (chloropropyl) phosphate , Tris (dichloropropyl) phosphate, ammonium polyphosphate, phosphorus-based flame retardants such as red phosphorus, magnesium hydroxide, antimony trioxide, inorganic flame retardants other than aluminum hydroxide such as antimony pentoxide, and heat-expandable graphite And the like. Catalyst In the present invention, a catalyst for the dehydrocondensation of component (B) and component (D) and the addition reaction (hydrosilylation reaction) between component (A) and component (B) can be used as appropriate. .

The hydrosilylation catalyst is not particularly limited, but chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of availability and catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited, but is preferably in the range of 10 ^-1 to 10 ^-8 mol, more preferably 10 ^-2 to 10 ^-6 mol, per 1 mol of the hydrosilyl group. .

A co-catalyst can be used in combination with the above-mentioned catalyst. One example is triphenylphosphine.

[0091] The amount of co-catalyst is not particularly limited, the catalyst 1 mol, preferably ^10-2 to ² mols, more preferably from 10 ^-1 to 10 mol. Other Components In addition to the above, the foamable resin composition of the present invention further comprises a solvent, a filler, an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, and a polydimethylsiloxane-polyalkylene oxide-based interface. Foam stabilizers such as surfactants or organic surfactants (eg, polyethylene glycol alkyl phenyl ether), storage stability improvers, ozone deterioration inhibitors, light stabilizers, thickeners, plasticizers, coupling agents, antioxidants, Heat stabilizers, conductivity imparting agents, antistatic agents, radiation blocking agents, nucleating agents, phosphorus-based peroxide decomposers, lubricants, pigments, metal deactivators, physical property modifiers, etc. It can be added within a range that does not impair.

In the present invention, it is preferable to use a blowing agent having a boiling point of 100 ° C. or lower as described above, but it is acceptable to use a solvent or a plasticizer having a boiling point of 100 ° C. or higher as an additive. Absent. Production of Cured Product and Foam A cured product can be produced by mixing the curable resin composition of the present invention in advance with an appropriate combination of a catalyst and, if necessary, an additive if necessary, followed by curing. The curing temperature is preferably 200 ° C. or lower, more preferably 100 ° C. or lower. At high temperatures exceeding 200 ° C, (A)
The rate of the curing reaction between the component and the component (B) becomes too high, and a deterioration reaction occurs, so that it is difficult to produce a molded body.

As a method for producing a cured product from the curable resin composition of the present invention, the curable resin composition of the present invention, a catalyst,
Further, a method is preferable in which two or more separate mixtures preliminarily mixed by appropriately combining additives as needed are mixed immediately before use, and extruded or poured.

The method for producing a foam from the foamable resin composition of the present invention includes a foamable resin composition of the present invention, a catalyst,
Further, if necessary, two or more separate mixtures preliminarily mixed by appropriately combining additives are mixed immediately before use, applied directly to the substrate surface, and foamed in situ, or a similar method. Preferably, the mixture is mixed immediately before use and injected and foamed.

As the mixing method, hand mixing,
Methods such as an electric mixer, a static mixer, and a collision mixing can be used. In particular, in the case of foaming in situ, it is preferable to use a static mixer or collision mixing.

The method of blending the components (A) and (B) in the curable resin composition and the foamable resin composition of the present invention is not particularly limited, but from the viewpoint of workability, (A)
After preparing two or more kinds of compositions each having a substantial component as the component and the component (B), it is preferable to cure them by mixing them. When aluminum hydroxide having an average particle diameter of 2 μm or more and 40 μm or less, which is the component (C), is preliminarily mixed, a composition containing the component (A) as a substantial component from the viewpoint of storage stability. Is preferably added. If the component (C) is added in advance to the composition containing the component (B) as a substantial component, the viscosity may increase with time.

The method of adding the catalyst is not particularly limited, and a method which is easy to work may be selected, and the components (A) and (B)
Any of the components may be used as a mixture, or they may be added simultaneously with the mixing of the components (A) and (B), or may be added after the completion of the mixing.

[0098] The method of molding the foam is not particularly limited, and may be used for polyurethane foam, phenol foam, silicone foam, etc., such as extrusion foaming, continuous foaming, cast molding, discontinuous molding, or in-situ foaming. The methods that have been developed can be used in an appropriate combination or partially modified so as to be applicable to the present invention.

The method for producing a foam for each of the above foams generally comprises a combination of a liquid feeding method for mixing the respective mixed components, a mixing method thereof, and a method of discharging the further mixed composition. It can be suitably used for various applications. Application Examples The curable resin composition of the present invention includes various molding materials, paints, powder coatings, spraying materials, protective coating materials, sealing materials, waterproofing materials, molding materials, casting rubber materials, adhesives, adhesive,
It can be used for vibration damping materials, contact adhesives, films and the like. Further, it can be used as a modifier for various thermoplastic resins or thermosetting resins. Further, the curable resin composition of the present invention can be used in various fields such as electronic and electric materials, civil and building materials, automobile and aircraft materials, optical materials, medical materials and the like.

Specific examples of electronic and electric materials include rigid wiring boards for semiconductor mounting, flexible printed wiring boards, mounting materials for semiconductor mounting, adhesives for flexible printed wiring boards, sealing resins for semiconductors, and electric and electronic parts. It can be used as a peripheral sealing material, a solar cell sealing material, an insulating film for a semiconductor, a coverlay film for protecting a flexible printed circuit, a coating agent for wiring coating, and the like. Specific examples of civil engineering and building materials include sealing agents, vibration-damping / vibration-proof materials, paints, adhesives, coating agent spraying agents, elastic wall materials, flooring materials, waterproofing agents, structural members, and the like. Further, specific examples of automobile / aircraft materials include sealants, sliding members, coating agents, underbody coats, structural members,
Adhesives, molding materials, and the like. Examples of the optical material include a core material and a clad material for an optical fiber, and a wear-resistant coating agent for a plastic lens.

As a medical material, it can be used for artificial bones, dental impression agents and the like. The fields of application and applications of the curable resin composition of the present invention are not limited to the fields described above.

The foamable resin composition of the present invention can be used for various purposes such as soundproofing, heat insulation, water stoppage, airtightness, vibration suppression, protection, cushion, decoration and the like.

[0103]

EXAMPLES Examples and comparative examples of the present invention are shown below.
The present invention is not limited by these. Synthesis Example 1,3,5,7-Tetramethylcyclotetrasiloxane (Shin-Etsu Chemical KF-9902) was placed in a four-necked flask connected with a dropping funnel, a cooling tube with a three-way cock connected to the top, a thermometer, and a mechanical stirrer. ) 120 g and toluene 200 ml were put, and heated to 40 ° C. while flowing an oxygen / nitrogen mixed gas (oxygen content 1%) from three cocks. P
13 mg of t-vinylsiloxane (3% xylene solution) was added, and 61.6 g of O, O'-diallylbisphenol A was added dropwise from a dropping funnel. Thereafter, a polyethylene oxide polymer having a terminal substituted with an allyl group and a methyl group (number average) 16.2 g of molecular weight (400) was added dropwise. 4 as it is
The mixture was stirred at 0 ° C. for 1 hour, and benzothiazole was added as a stabilizer. The obtained liquid was depressurized at 60 ° C., and toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off to obtain a viscous transparent liquid (B-1). Examples 1 to 3 and Comparative Examples 1 to 4 First, the components (A) and (C) were mixed by the amount shown in Table 1, and the viscosity of the obtained compound was measured using a BM type viscometer manufactured by Tokyo Keiki. In a constant temperature room at a temperature of 23 ° C. and a humidity of 50 ± 10%, no. The measurement was performed under the conditions of 4 spindles and a rotation speed of 6 rpm. Also, put these formulations in a glass bottle,
After storage at 0 ° C. for one day, the appearance was checked for sedimentation (storage stability). As shown in Table 1, as components (A), O, O'-diallylbisphenol A and 2,2'-
Using diallyl bisphenol A, aluminum hydroxide having an average particle diameter of 2 μm or more and 40 μm or less as a component (C), manufactured by Showa Denko K.K.
4 (average particle diameter, about 3.5 μm) and trade name Heidilite H-32 (average particle diameter, about 8 μm). Also,
As a comparison of the component (C), aluminum hydroxide having an average particle size of less than 2 μm, manufactured by Showa Denko KK, trade name Hygilite H-42M (average particle size, about 1 μm), water having an average particle size larger than 40 μm As the aluminum oxide, HYGILIGHT H-10 (average particle size, about 55 μm) manufactured by Showa Denko KK was used.

Next, the components (A) and (C) described above and the component (B) obtained by the above synthesis example were mixed in the amounts shown in Table 1, and then mixed with Pt-vinylsiloxane (3% xylene solution). ) Was added in the amounts shown in Table 1 and stirred at 23 ° C., and in each case, the composition was cured with heat generation, and a hard cured product was obtained. At this time, ease of handling (workability) at the time of stirring was comparatively evaluated. After leaving the obtained cured product at room temperature for one week, the limiting oxygen index was measured according to JIS K7201. The evaluation results of viscosity, storage stability, workability, and limiting oxygen index are shown in Table 1 together with the formulation.

[0105]

[Table 1] As can be seen from Table 1, the average particle diameter is 2 μm or more and 40 μm or more.
Examples 1 to 3 containing not more than m aluminum hydroxide
Has good storage stability without sedimentation over time, does not greatly reduce workability, and has markedly improved flame retardancy as compared with Comparative Example 1 in which the component (C) was not added. I have.
On the other hand, in Comparative Examples 2-3 containing aluminum hydroxide (Heidilite H-42M) having an average particle diameter of less than 2 μm, the viscosity was high and workability was significantly reduced, and aluminum hydroxide having an average particle diameter of 40 μm or more was used. (Heidi Light H
In Comparative Example 4 containing -10), sedimentation over time was observed, and storage stability was poor. Examples 4 to 7 and Comparative Examples 5 to 8 In the same manner as described above, the components (A) and (C) were mixed in amounts shown in Table 2, and the viscosity of the resulting blend was measured. In addition, the presence or absence of sedimentation (storage stability) after storage at 50 ° C. for one day was confirmed.

Next, after the components (A) to (D) were mixed in accordance with the recipe shown in Table 2, the Pt-vinylsiloxane (3
% Xylene solution) was added as shown in Table 2 and stirred at 23 ° C. In each case, foaming was generated with heat generation, and a hard foam was obtained. At this time, ease of handling (workability) at the time of stirring was comparatively evaluated. After leaving the obtained foam at room temperature for one week, the limiting oxygen index was measured according to JIS K7201. Table 2 shows the evaluation results of viscosity, storage stability, workability, and limiting oxygen index together with the formulation.
Shown in

[0107]

[Table 2] As can be seen from Table 2, the average particle diameter is 2 μm or more and 40 μm or more.
Examples 4-7 containing up to m aluminum hydroxide
Has good storage stability without sedimentation over time, does not greatly reduce workability, and has a markedly improved flame retardancy as compared with Comparative Example 5 in which the component (C) is not added. I have.
On the other hand, in Comparative Examples 6 to 7 containing aluminum hydroxide (Heidilite H-42M) having an average particle diameter of less than 2 μm, the viscosity was high and workability was significantly reduced, and aluminum hydroxide having an average particle diameter of 40 μm or more was used. (Heidi Light H
In Comparative Example 8 containing -10), sedimentation over time was observed, and storage stability was poor.

[0108]

According to the first to sixth aspects of the present invention, it has good workability and storage stability, can be cured at room temperature or at a relatively low temperature, and can be cured. A curable resin composition and a cured product having excellent flame retardancy can be obtained.

According to the invention as set forth in claims 7 to 10, the foamed material has good workability and storage stability, can be foamed and hardened under heating at room temperature or at a relatively low temperature, and can be obtained. Can obtain a foamable resin composition and a foam having excellent flame retardancy.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/06 C08L 71/00 A 71/00 83/12 83/12 101/02 101/02 C08K 5 / 54 C

Claims (10)

[Claims] 1. An organic compound having (A) a carbon-carbon double bond, (B) a compound having a SiH group, and (C) aluminum hydroxide having an average particle diameter of 2 μm or more and 40 μm or less. Curable resin composition. 2. The organic compound of component (A) is selected from phenolic compounds having one or more carbon-carbon double bonds in one molecule, bisphenolic compounds, polyether polymers, and polyester polymers. The curable resin composition according to claim 1, wherein: 3. The composition according to claim 1, wherein the component (B) is a compound containing a chain and / or cyclic organosiloxane having one or more SiH groups in one molecule. Or the curable resin composition according to item 2. 4. The component (B) has at least one SiH group in one molecule and is selected from styrene derivatives, phenol derivatives, bisphenol derivatives, polyether derivatives, polyester derivatives and olefin derivatives. 1
The curable resin composition according to claim 1, wherein the curable resin composition is a chain and / or cyclic organosiloxane having in its molecule a skeleton introduced from at least one kind of compound. 5. A total amount of the components (A) and (B) of 10
The curable resin composition according to any one of claims 1 to 4, wherein the curable resin composition contains the component (C) in an amount of 1 to 200 parts by weight with respect to 0 parts by weight. 6. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5. 7. The curable resin composition according to claim 1, further comprising (D) a foaming agent and / or a compound having an OH group. Foamable resin composition. 8. The foaming agent of component (D) has a boiling point of 100 ° C.
8. The volatile compound according to claim 7, wherein:
Item 10. The foamable resin composition according to item 7. 9. The compound according to claim 7, wherein the compound having an OH group as the component (D) is an organic compound in which the OH group is directly bonded to a carbon atom and / or water. The foamable resin composition as described in the above. 10. A foam obtained by subjecting the foamable resin composition according to any one of claims 7 to 9 to foaming and curing.