JP3146020B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel curable resin composition, and more particularly to a curable resin composition capable of imparting excellent mechanical properties, weather resistance and heat resistance, particularly hydrolysis resistance, to a cured product. About things.

[0002]

2. Description of the Related Art Conventionally, various types of room temperature curable resin compositions have been developed, but curable resins capable of imparting excellent mechanical properties, weather resistance and heat resistance to cured products. Few compositions have been developed.

[0003] A composition comprising a polyester as the main chain can be expected to have excellent mechanical properties, weather resistance and heat resistance in a cured product. For example, a curable resin composition comprising polycaprolactone is known from Japanese Patent Publication No. 49-32673, but cannot be used as an elastic body because the resulting composition is crystalline. In Japanese Patent Application Laid-Open No. 62-15225, a liquid type polycaprolactone is used to compensate for this disadvantage, but since a bulky group is introduced into the main chain in order to make it amorphous, Sufficient properties have not been obtained. In addition, since the main chain is made of polyester, it has a drawback that it has poor hydrolysis resistance.

[0004]

An object of the present invention is to provide a curable resin composition capable of imparting excellent mechanical properties, weather resistance, heat resistance, and especially hydrolysis resistance to a cured product. is there. That is, the present invention

(A) At least one silicon atom-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter referred to as “reactive silicon group”). And a main chain containing a repeating unit represented by-(-R-OC (= O) O-)-wherein R is a hydrocarbon group having 4 to 20 carbon atoms. ,
And (B) a curable resin composition containing a silanol condensation catalyst. Here, the reactive silicon group is not particularly limited, but typical examples include a group represented by the following general formula (1). _{^{- [- Si (-R 1 2}} -b) (- X b) -O-] m -Si (-R 2 3-a) -X a (1)

In the formula, R ¹ And R ² Each have 1 carbon atom
To 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ') ₃ SiO
-[R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Three R's may be the same or different], and R ¹ represents a triorganosiloxy group; Or R ² When two or more are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a is 0, 1, 2
Or 3 and b represents 0, 1 or 2. Also, m
Number of _{^{-Si (-R 1 2-b)}} (- X b) -O- b need not be the same in the group. m represents 0 or an integer of 1 to 19. However, it is assumed that a + (sum of b) ≧ 1 is satisfied.

The hydrolyzable group represented by X is not particularly limited, but includes a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among them, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group,
Aminooxy, mercapto and alkenyloxy groups are preferred. An alkoxy group is particularly preferred from the viewpoint that the hydrolyzability is mild and easy to handle.

This hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 and a + (the sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

The number of silicon atoms forming the reactive silicon group may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, up to about 20 silicon atoms are used. Is also good. In particular, equation _{^{(2) -Si (-R 2 3}} -a) -X a (2) [ wherein, R ² , X, and a are the same as those described above].

Further, R ¹ in the above general formula (1) And R ² Specific examples of the above include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and a group in which R ′ is a methyl group or a phenyl group. And the like (R
') Triorganosiloxy group and the like represented by ₃ SiO-. Of these, a methyl group is particularly preferred.

It is preferable that at least one, preferably 1.1 to 5 reactive silicon groups be present in one molecule of the polymer.
If the number of reactive silicon groups contained in the molecule is less than one, the curability will be insufficient and it will be difficult to exhibit good rubber elasticity behavior.

The reactive silicon group may be present at the terminal of the polymer molecular chain, may be present internally, or may be present at both. Particularly when the reactive silicon group is present at the terminal of the molecular chain, the effective network chain amount of the polymer component contained in the finally formed cured product becomes large, so that the rubbery cured product having high strength and high elongation is obtained. Is preferred from the viewpoint of easily obtaining

The polymer used in the present invention preferably has a number average molecular weight of 3,000 or more. Molecular weight 3,
If it is less than 000, sufficient elongation cannot be obtained, and fracture occurs before sufficient strength is developed. Therefore, in order to obtain sufficient mechanical strength, the molecular weight needs to be 3,000 or more. There is no particular upper limit, but 2
Those up to 000 are particularly preferred. The main chain of the polymer used in the present invention is-(-R-OC (= O) O-)-, wherein R is a hydrocarbon having 4 to 20 carbon atoms.

A polycarbonate polymer containing a repeating unit represented by the formula (1), preferably an aliphatic polycarbonate polymer having a molecular weight of 3,000 or more. This polycarbonate polymer is, for example, transesterified with a carbonate such as dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and a polyhydroxy compound such as 1,6-hexanediol, 1,4-butanediol, cyclohexanedimethanol. It can be obtained by reacting. Also, copolymers with components other than these components for imparting amorphousness are known. Commercially available products include Desmophen 2020E of Bayer, Carbodiol D-1000 and D-2000 of Toa Gosei Chemical, Nipporan 980, 981, 982, 9 of Nippon Polyurethane.
83. There is the PLACCEL CD series of Daicel Chemical. These have a molecular weight of 1,000 to 2,000.
0. These readily available molecular weights of 1,000
Those having a molecular weight of 0 to 2,000 can be reacted with an organic compound having two or more active groups having reactivity to terminal hydroxyl groups to jump the molecular weight to obtain a large molecular weight. For example, it can be easily obtained by reacting isophthalic acid chloride in the presence of an amine such as triethylamine or pyridine.

The introduction of a reactive silicon group into the above-mentioned polymer may be carried out by a known method. For example, a polymer having a functional group such as a hydroxyl group at a terminal may be added to an active group having a reactivity with the above-mentioned functional group. And an organic compound having an unsaturated group, and then reacting the resulting reaction product with hydrosilane having a hydrolyzable group to effect hydrosilylation. Hydrosilane of the general formula (3) H-Si (-R 3 3-a) -X a (3)

[Wherein R ³ Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. When two or more are present, they may be the same or different. May be. X represents a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a represents 0, 1, 2 or 3. ]

## EQU1 ## This is, for example, H ₂ Pt
Cl ₆ · 6H ₂ O, Pt metal, RhCl (PPh _3)
3 , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , Ir
_{Cl 3, FeCl 3, AlCl 3} , PdCl 2 · 2H 2
By performing a hydrosilylation reaction using a compound such as O, NiCl ₂ , or TiCl ₄ as a catalyst, a reactive silicon group can be introduced.

The hydrosilylation reaction is generally carried out at 0 ° C to 1 ° C.
The reaction is performed in a temperature range of 50 ° C., and a solvent such as benzene, toluene, xylene, or tetrahydrofuran may be used as necessary, for example, for adjusting the reaction temperature and adjusting the viscosity of the reaction system.

In order to make the curable resin composition of the present invention a cured product, it is necessary to condense a hydrolyzable group with a silanol condensation catalyst. Specific examples of the silanol condensation catalyst include, for example, titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; Reaction product of dibutyltin oxide and phthalic acid ester; dibutyltin diacetylacetonate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetra Chelating compounds such as acetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanol Amine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) Amine compounds such as phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acids and the like A low molecular weight polyamide resin obtained from an excess of a polyamine and a polybasic acid; a reaction product of an excess of a polyamine with an epoxy compound; a silane coupling agent having an amino group, for example, γ-aminopropyltrimethoxysilane, N- ( β-a Examples thereof include silanol condensation catalysts such as minoethyl) aminopropylmethyldimethoxysilane, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

These catalysts may be used alone,
More than one species may be used in combination. When a curing catalyst is used, the amount is preferably 0.1 to 20 parts, more preferably 1 to 10 parts, per 100 parts of the polymer. If the amount of the curing catalyst used is too small, the curing rate becomes slow and the curing reaction does not proceed sufficiently, which is not preferable. On the other hand, if the amount of the curing catalyst is too large, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product, which is not preferable.

The composition of the present invention may further contain, if necessary,
Adhesion modifier, physical property modifier, storage stability modifier, plasticizer, filler, antioxidant, ultraviolet absorber, metal deactivator, ozone deterioration inhibitor, light stabilizer, amine radical chain inhibitor Various additives such as a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added.

[0022]

EXAMPLES In order to further clarify the present invention, examples will be described below. Example 1

PLACCE manufactured by Daicel Chemical Industries, Ltd.
300 g of L CD-220PL (molecular weight about 2,000)
Was weighed into a four-necked flask and azeotropically dehydrated with a small amount of toluene to remove water in the system. 400 ml of toluene dried with molecular sieves and 30 ml of pyridine were added. Next, isophthalic acid chloride 23.4
g was dissolved in toluene and added to the system via a dropping funnel.
After the completion of the dropwise addition, the reaction temperature was raised to 60 ° C., and the reaction was carried out for 1 hour. Cooled to around room temperature, allyl chloroformate 16.3
ml was added and the reaction was performed again at 60 ° C. for 1 hour. After the reaction, the precipitated salt and pyridine were removed by washing with water,
By drying and removing the solvent, an allyl-terminated polycarbonate having a jumped molecular weight (set molecular weight: 8,000) was obtained. From the iodine value of the obtained allylic compound, the amount of allyl groups was 0.0339 mol / 100 g.

200 ml of toluene dried with molecular sieves was added to the obtained allyl group-terminated polycarbonate to lower the viscosity of the system, and 0.1 ml of a 10% ethanol solution of chloroplatinic acid was added. Dimethyltrimethoxysilane 30
ml was added by a dropping funnel and reacted at 80 ° C. for 1 hour to obtain a polycarbonate having a reactive silicon group at the end.

To 100 parts of the obtained polycarbonate, 3 parts of an antioxidant [1 part of Sanol (Sankyo), 1 part of Tinupin 327 (Ciba-Geigy), 1 part of Irganox 1010
(Ciba-Geigy) 1 part], 3 parts of tin octylate and 0.75 part of laurylamine were blended as a curing catalyst,
Cured at 50 ° C. for 4 days to produce a cured product.

The results of the tensile properties of the obtained cured products are shown in Table 1.
It is shown in FIG. Table 2 shows the results of the heat resistance test conducted by placing the cured product in a 130 ° C. oven. Table 3 shows the results of the weather resistance test using the sunshine weather meter.
Table 4 shows the results of the hydrolysis resistance test using hot water at 80 ° C.

In these tables, M10, M30, M
50, M100, and M150 indicate the modulus at 10% elongation, the modulus at 30% elongation, the modulus at 50% elongation, the modulus at 100% elongation, and the modulus at 150% elongation, respectively, and TB and EB indicate breaking strength and breaking, respectively. Indicates elongation. Table-1 Dumbbell tensile properties M10 M30 M50 M100 M150 TB EB kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² (%) 2.1 4.2 5.4 7.1 8.5 24.7 497 Table-2 130 ° C. heat resistant dumbbell test result M10 M30 M50 M100 M150 TB EB kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² (%) Initial 2.1 4.2 5.4 7.1 8.5 24.7 497 After 300 hours 1.7 3.6 4.7 4.7 6.3 7.7 24.0 467 After 500 hours 1. 6 3.6 4.7 6.3 7.7 20.6 407 After 1000 hours 1.7 3.5 4.6 6.2 7.6 19.6 464 After 2000 hours 1.6 3.4 4.4. 5 6.1 7.5 24.1 581 After 3000 hours 1.7 3.6 4.7 4.7 6.4 7.8 27.2 585 After 5000 hours 2.9 4.3 5.2 7.0 8.0 7 16.6 352 Table-3 Weather dumbbell test result M10 M30 M50 M100 M150 TB EB kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² (%) Initial 2.1 4.2 5.4 7.1 8.5 24.7 497 After 300 hours 1.7 3.6 4.8 6.5 6.5 8.1 22.5 531 After 1000 hours 1. 7 3.7 4.9 6.6 8.1 15.5 343 After 2000 hours 1.7 3.7 4.9 6.7 8.1 16.8 390 After 3000 hours 2.0 3.9 5. 0 6.8 8.3 17.5 374 Table-4 Results of 480 ° C. hot water resistant dumbbell test M10 M30 M50 M100 M150 TB EB kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² kg / cm ² (%) Initial 2.1 4.2 5.4 7.1 8.5 24.7 497 2 days later 1.9 3.8 4.9 6.6 8.0 19.1 385 4 days later 1.4 2 3.9 3.8 5.1 6.2 31.1 621 After 7 days 1.1 2.6 3.4 4.6 5.5 31.8 714 After 14 days 1.1 2.2 2.8 3.7 4.4 33.7 819 30 days later 0.7 1.7 2.3 3.0 3.6 29.6 876 90 days later 0.7 1.4 1.8 2.2 2.6 35.3 1073

As is clear from these tables, the cured product obtained from the curable resin composition of the present invention exhibited excellent mechanical properties, weather resistance and heat resistance. In particular, a cured product having excellent hydrolysis resistance was obtained.

[0029]

The cured product obtained from the curable resin composition of the present invention has excellent mechanical properties, weather resistance and heat resistance, and particularly has excellent hydrolysis resistance.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumi-ku, Kobe-shi, Hyogo (56) References JP-A-2-311565 (JP, A) JP-A-1-75524 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/42 C08L 69/00

Claims (1)

(57) [Claims] (A) having at least one silicon atom-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond; -R-OC (= O) O-)-wherein R is a hydrocarbon group having 4 to 20 carbon atoms, a polycarbonate polymer containing a repeating unit represented by the formula: (B) a silanol condensation catalyst, and (C) A curable resin composition which gives an elastic body and contains an antioxidant.