JPH02153963A - Cold-setting resin composition - Google Patents

Abstract

PURPOSE:To obtain a cold-setting resin composition capable of giving a cured material having high hardness even under highly humid condition by compounding a composition containing a specific linear polymer and a hydrolyzable silane compound having epoxy group with a specific curing agent. CONSTITUTION:The objective composition is produced by compounding a composition composed mainly of (A) a linear polymer having Si bonded to a hydrolyzable group at the terminal of a side chain or chain molecule (preferably copolymer of glycidyl methacrylate and vinyltrimethoxysilane, etc.) and (B) a hydrolyzable silane compound having epoxy group with (C) a curing agent composed mainly of a hydrolyzable silane compound of formula (R<1> and R<2> are H, alkyl, etc.; R<3> is 3-6C alkylen, etc.; X is 3-6C univalent hydrocarbon group; Y is <=6C alkyl or alkoxyalkyl; a is 0 or 1) and, as necessary, (D) a hydrolyzable silane compound (e.g. ethyl silicate) as a crosslinking agent for alkocysilane and a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a room temperature curable resin composition, and more particularly to a room temperature curable resin composition that is particularly useful as a coating material that provides a cured product with high hardness.

(Prior art) Conventionally, room-temperature-curing paints have been mainly used for woodworking, plastics, etc. For example, for woodworking, two-component reaction-type paints containing acrylic polyol as the main ingredient and polyisocyanate prepolymer as the curing agent have been used. There is acrylic urethane paint.

In addition, as a room-temperature curing composition containing a silicon compound, a composition consisting of a vinyl resin containing a hydrolyzed silyl group at the terminal or side chain and a curing catalyst (Japanese Patent Application Laid-Open No. 57-17295
(Japanese Patent Laid-Open No. 157810/1982) are known.

Furthermore, in a vinyl polymer having a basic nitrogen atom, a compound having an epoxy group and a hydrolyzable silyl group in one molecule as a curing agent and a hydrolyzable silyl group without containing an epoxy group as all essential groups. A composition comprising a compound containing a silanol group and/or a compound containing a silanol group (2) is also known.

(Problems to be Solved by the Invention) In recent years, there has been a desire to develop high-hardness wood paints in order to prevent scratches on the surfaces of high-end furniture.Also, in the field of plastics, higher hardness paints have been desired. There is a need for a room-temperature curing coating that provides the following properties.

However, the cured product obtained using the conventional composition has insufficient hardness (1) and insufficient low temperature curing.
Another problem is that the hardness is easily affected by humidity, and the hardness decreases significantly especially under high humidity.

An object of the present invention is to provide a room-temperature curable resin composition that has significantly improved hardness compared to cured products obtained using conventional compositions, and that allows a cured product with high hardness to be obtained even under high humidity. It is.

(Means for Solving the Problems) The present invention comprises a linear polymer having a silicon atom bonded to a hydrolyzable group at the end of a side chain or a chain molecule, and a hydrolyzable silane compound containing an epoxy group. The polymer composition as the main component and the general formula % formula % where R1 and R1 are each a hydrogen atom or an alkyl group,
selected from the group consisting of an alkenyl group, an alkynyl group, an aryl group, a cyanoalkyl group, a trifluoropropyl group, and a halophenyl group, and R3 is an alkylene group having 3 to 6 carbon atoms or an alkylene group having the following formula %, Q is a monovalent hydrocarbon group having 3 to 6 carbon atoms, %Y is an alkyl group or an alkoxyalkyl group having 6 or less carbon atoms, and a is a value of 0 or 1. ) A curing agent (g) whose main component is a hydrolyzable silane compound (B-1) represented by:

The polymer having a silicon atom bonded to a hydrolyzable group at the end of a side chain or chain molecule, which is a main element constituting the composition of the present invention, is a polymer having a free carbon-carbon double bond. However, it can also be prepared by introducing a silicon atom having a hydrolyzable group into the monomer through a hydrosilylation reaction between this and a silane compound having a hydrogen atom bonded to silicon and a hydrolyzable group. It is convenient and preferable to prepare by copolymerization of a compound having a polymerizable double bond and no silicon atom and a silane compound having a polymerizable double bond and a hydrolyzable group.

Next, the hydrolyzable silane compound (B-1), which is the main component of the curing agent (B), is made from allylamine and a carbonyl compound with the general formula % (in the formula, R1 and R2 each have the same meaning as ), and by introducing a silicon atom having a hydrolyzable group into the ketimine compound through a hydrosilylation reaction between this and a silane compound having a silicon-bonded hydrogen atom and a hydrolyzable group. Although it is also possible to prepare the compound by reacting a hydrolyzable clan compound containing an amino group with a carbonyl compound, it is convenient and preferred. However, it is necessary to have an appropriate dehydrating agent in the reaction system to prevent condensation of hydrolyzable groups due to the generated water, or to quickly remove the generated water by an azeotropic dehydration method, etc. .

Among the raw materials used in the present invention, typical compounds having a polymerizable double bond and no silicon atom include glycidyl methacrylate, glycidyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, lauryl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, etc. In addition to methacrylic acid esters and acrylic esters, methacrylic acid, acrylic acid, acrylonitrile, fumaric anhydride, styrene,
Examples include vinyl toluene aromatics and vinyl monomers.

Typical examples of the silane compounds having a polymerizable double bond and a hydrolyzable group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, etc. can be mentioned.

In addition, examples of hydrolyzable silane compounds containing epoxy groups include 3-glycidoxyprobyltrimethoxysilane,
3-glycidoxypropylmethyldimethoxysilane, 2
Typical examples include -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, but 3-glycidoxypropyltrimethoxysilane is particularly desirable from the viewpoint of curability.

Next, as the hydrolyzable silane compound containing an amino group, N-(2-7minoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)
-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.

The carbonyl compound has the general formula % (in the formula, R9 and R10 each represent the same meaning as R1).
It is expressed as

The room temperature curable resin composition of the present invention may also contain an appropriate amount of a hydrolyzable silane compound as an alkoxysilane crosslinking agent.

The silane compound can be mixed with either or both of the polymer composition (2), the curing agent (B), or a mixture thereof.

Examples of the hydrolyzable silane compound as the alkoxysilane crosslinking agent include alkyl silicates such as ethyl silicate and methyl silicate, partially hydrolyzed condensates of alkyl silicates, and alkyl silanes of which methyltrimethoxysilane is a representative example. Examples include trialkoxysilane, alkenyltrialkoxysilane of which vinyltrimethoxysilane is a typical example, phenyltrialkoxysilane of which phenyltrimethoxysilane is a representative example, and partially hydrolyzed condensates of the triplekoxysilanes. .

Next, a method for producing the room temperature curable resin composition 'IJ' of the present invention will be explained.

First, the polymer composition (4) is preferably a compound having a monopolytic double bond and no silicon atom (hereinafter referred to as "vinyl X
It is called "L-mer". ) and a silane compound having a polymerizable double bond and a hydrolyzable group (hereinafter "polymerizable silane compound")
That's what it means. ) to prepare a linear copolymer having a silicon atom bonded to a hydrolyzable group at the end of a chain or chain molecule, and a hydrolyzable silane compound containing an epoxy group in the polymer. obtained by mixing. In the copolymerization, the proportion of the polymerizable silane compound in the total monomers (i.e., the total amount of the vinyl monomer and the polymerizable silane compound) is 1 to 30% by weight, preferably 5 to 2011% by weight. It is best to copolymerize so that the
The mixing ratio of the hydrolyzable silane compound containing the epoxy base to the copolymer is preferably 0.1 to 1.0, preferably 0.3 to 0.7 in terms of weight ratio. Conditions outside these ranges, whether below the lower limit or exceeding the upper limit, may cause a decrease in the stability of the resin composition of the present invention or a decrease in the hardness of the cured product of the composition, or This is not preferred because it tends to cause deterioration in the appearance of the paint film such as whitening.

Any conventionally known polymerization method can be applied to the copolymerization of the vinyl monomer and the polymerizable silane compound, but radical polymerization in an organic solvent is the simplest and easiest method.

The organic solvent to be removed may be an inert organic solvent as long as it does not affect the stability of each compound used in the present invention or each reaction in producing the composition of the present invention.
This is advantageous in that the copolymerization reaction can be controlled easily and smoothly. Examples of such solvents include toluene, xylene, cyclohexane, n-hexane, and various hydrocarbons such as high-boiling aromatic hydrocarbon bath agents, such as "Swazol" (trademark) manufactured by Maruzen Sekiyu, Methanol, ethanol, isobutanol, n-propertool, n
-Alcohols such as butanol, isobutanol, 3-butanol, ethylene glycol 7-methyl ether,
Examples include esters such as methyl acetate, ethyl acetate, n-butyl acetate, and ethylselonupacetate, and these can be used alone or in combination.

Next, to make the curing agent (B)', first, a hydrolyzable silane compound containing an amino base is reacted with a carbonyl compound, and the water produced at that time is removed with a dehydrating agent or by azeotropic dehydration. Silane compound (B-1
)t-manufacture. Examples of the dehydrating agent used at this time include various zeolites such as Molecular Sheeps.

The hydrolyzable silane compound (B-1) produced in this way is used as an essential component, and if necessary, the above-mentioned organic solvents are added thereto and mixed to FAR the curing agent. At this time, alkyl silicates such as methyl silicate and ethyl silicate, or partially hydrolyzed condensates of the alkyl silicates, or alkyltrialkoxysilanes such as methyltrimethoxysilane, and alkenyls such as vinyltrimethoxysilane are used. Addition of hydrolyzable alkoxysilanes such as phenyltrialkoxysilanes, all representative examples of trialkoxysilanes and phenyltrimethoxysilanes, or partially hydrolyzed condensates of the trialkoxysilanes, as an alkoxysilane crosslinking agent. You can also do it. The amount to be used at this time is not limited, but it is preferable that the ratio of N to the hydrolyzable silane compound (B-1) as the main component is from 1/10 to 172.

Hydrolyzable alkoxysilanes as alkoxysilane crosslinking agents can be used by adding them to the polymer composition (4) instead of the curing agent CB), or alternatively, they can be used by adding them to the polymer composition (4) as well as the curing agent. ) may be added to both.

Although the room-temperature curable resin composition of the present invention has good curability even without the addition of a facilitation catalyst, it is possible to use a catalyst for hydrolyzing and condensing each of the hydrolyzable silane compounds described above. Therefore, it is possible to accelerate the curing reaction and further improve low-temperature curability. Such hydrolytic condensation catalysts (typical examples include basic compounds such as sodium hydroxide, potassium hydroxide, sodium methylate or tetramethylammonium hydride, tetraisopropyltitanate, aluminum acetylacetone, octylic acid) Metal salts of organic acids such as lead, zinc octylate, calcium octylate, lead naphthenate, diptyltin diacetate, dibutyltin dilaurate, or dibutyltin simalate; There are acidic compounds, etc.

This hydrolytic condensation catalyst Q may be used in addition to the curing agent (B) or the alkoxysilane crosslinking agent, or may be a mixture of the polymer composition initial and curing agent (B) or the polymer composition initial, curing agent (B). It may be added to a mixture of alkoxysilane and alkoxysilane crosslinkers.

The room-temperature curable resin composition of the present invention is prepared by combining the polymer composition prepared as described above and the curing agent (B) such that the ratio of epoxy groups to >C-N- groups contained in each component is epoxy. The polymer composition (4) is mixed with a hydrolytic condensation catalyst as a component C, if necessary, so that the molar ratio of the C-N-group to the C-N group is 0.8 to 3.0. It is preferable to manufacture by adding about 0.001 to 1% by weight based on the total amount of the curing agent mixture including the solvent and the curing agent mixture.

The room temperature curable resin composition of the present invention may further contain various additives such as organic or inorganic dyes and pigments, matting agents, ultraviolet absorbers, fillers, and fluid FA agents. However, there is no problem unless these additives impair the curing reaction of the room-temperature curable resin composition of the present invention.

The room temperature curable resin composition of the present invention is applied to various substrates and then dried at room temperature to give a cured product with high hardness. This does not preclude heating, nor does it diminish the benefits obtained.

The room temperature curable resin composition of the present invention obtained as described above can be widely used as a paint, a surface modifier, a filler, etc. for wood products, various plastic products, etc.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

In addition, in the following examples, all parts and percentages are based on production volume unless otherwise specified.

(Preparation of Polymer Composition (2)) 100 parts of xylene and 50 parts of n-butanol were charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the mixture was heated under a silicon atmosphere. After raising the temperature to 90°C, 55 parts of methyl methacrylate, 20 parts of glycidyl methacrylate, 15 parts of n-butyl methacrylate, and 3-methacryloxypyltrimethoxysilane (hereinafter referred to as rMOPS-M) were added.
It is abbreviated as. ) 10 parts and peroxide catalyst (NOF e+
A liquid mixture consisting of 2.5 parts of the product, [Niper BMT J (registered trademark) (peroxide 20%)] was added dropwise over 3 hours. After the dropwise addition was completed, the same temperature was maintained for 3 hours to obtain a solution of polymer composition (A-1) having a resin content of 40%. Add 100 parts of this polymer (A-1) solution to 3-glycidoxyprobyltrimethoxysilane (hereinafter referred to as 1"GP8-M).
It is abbreviated as J. ) were mixed to obtain an initial solution of the polymer composition. This solution 'kl [is referred to as the combined composition (IA).

v4#! Examples 2-4 Use of vinyl monomer and polymerizable silane compound i (part)
Polymers (A-2) to (A-4) were obtained in the same manner as in Preparation Example 1, except for changing as shown in Table 1. Add GP to 100 parts of each of the solutions of polymers (A-2) to (A-4).
S-Mt-Polymer composition (
2A) to (5A) were obtained.

Table 1 However, MMA: Methyl methacrylate GMA Nigericidyl methacrylate c) (MA- Nidichlohexyl methacrylate BMA Nibutyl methacrylate LMA: Lauryl methacrylate Table 2 Preparation of the composition of polymer composition A (of the curing agent mixture) ) 7100 parts of 4-methyl-2-pentano and 100 parts of Molecular Sheeps 3A (trademark) were charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, and the mixture was heated to 80°C under a nitrogen atmosphere. After heating, add 3-aminopropyltriethoxysilane (hereinafter referred to as rAPS-EJ) 12
0 part was added dropwise over 2 hours. After the completion of the dropwise addition, the bales were kept at the same temperature for 5 hours, and the reaction mixture was distilled to remove 4-methyl-2-pentanone and APS-Eft. Another fraction was incubated at a temperature of 112-116 °C for 3-4 tlH.
Compound (IB)' was obtained by collecting under a pressure of 100 g. Analysis by gas chromatography shows that the liquid is 98% pure, and the trace material 4-methyl mass spectrum shows the structure: caacite N-CHtCHtCHt-8i (OCLCH
s)! ? Ht CH=CHs ” Hs.

90 parts of this compound (IB) was partially hydrolyzed with ethyl silicate 1 Nippon Colcoat #! ES-40 (registered trademark)) to form a curing agent mixture (2B)t.
- dibutyltin diacetate as catalyst C).
1 part was added and mixed to prepare a curing agent mixture (3B).

Examples 1 to 4, Comparative Example 1.2 Polymer compositions (IA) to (5A) obtained in Preparation Examples 1 to 5
) was diluted to an active ingredient concentration of 35% by adding a 1:1 mixed solvent of toluene and butyl acetate, and then hardening agents (IB) to (3B) were added to 100 parts of this diluted solution as shown in Table 3. A curable resin composition was prepared by adding and mixing the amounts shown in Table 4.

Next, this curable resin composition was applied to a glass plate with a bar coater so that the dry film thickness was about 10 μm, and the relative humidity was adjusted to 79% with a saturated solution of NH4C1 under normal temperature and high temperature conditions. It was cured in a desiccator at ℃ to obtain each cured coating film. In order to evaluate the surface scratch resistance of each coating film thus obtained, pencil hardness was measured. The results are shown in Tables 3 and 4.

Table 1 (Note) Pencil hardness: Measured according to the 8.4 pencil hardness test of JIS G-3312 (colored zinc plate), and the maximum hardness without scratching the surface is indicated.

ζHere, Comparative Example 1 is an example in which the hydrolyzable silane compound containing an epoxy group is absent in the initial polymer composition, and Comparative Example 2 is an example in which the copolymer is hydrolyzable among the constituent elements in the initial polymer composition. These examples lack a silicon atom bonded to a group, and each has drawbacks such as low coating film hardness or poor coating film appearance.

(Effects of the Invention) As is clear from the above examples, the present invention made it possible to obtain a cured product with high hardness at room temperature and even under high humidity. This provides a highly hard paint for wood or plastics, and the industrial benefits are immeasurable.

that's all

Claims (5)

[Claims] (1) A polymer composition (A ) and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ {In the formula, R^1 and R^2 are each a hydrogen atom or an alkyl group,
selected from the group consisting of an alkenyl group, an alkynyl group, an aryl group, a cyanoalkyl group, a trifluoropropyl group, and a halophenyl group, and R^3 is an alkylene group having 3 to 6 carbon atoms or the following formula ▲ Numerical formula, chemical formula, table etc. ▼ (In the formula, R^4 and R^5 are alkylene groups each having 1 to 6 carbon atoms, and Q is the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^6 and R^ 7, R^8 each has the same meaning as R^1. ) is a group represented by ), X is a monovalent hydrocarbon group having 3 to 6 carbon atoms, Y is a carbon an alkyl group or an alkoxyalkyl group having up to 6 atoms, and a represents a value of 0 or 1; } A room temperature curable resin composition comprising a curing agent (B) containing a hydrolyzable silane compound (B-1) represented by the formula (B-1) as a main component. (2) A cold-curable resin composition obtained by mixing the polymer composition (A) according to claim (1), a curing agent (B), and a hydrolyzable silane compound as an alkoxysilane crosslinking agent. (3) Room-temperature curing obtained by mixing a catalyst for promoting hydrolysis and condensation of a hydrolyzable silane compound in addition to the two components described in claim (1) or the three components described in claim (2). resin composition. (4) A linear polymer having a silicon atom bonded to a hydrolyzable group at the end of a side chain or a chain molecule has a polymerizable double bond and a compound having no silicon atom has a polymerizable double bond and a silane compound having a hydrolyzable group. (5) The room temperature curable resin composition according to any one of claims (2) to (4), wherein the hydrolyzable silane compound as the alkoxysilane crosslinking agent is ethyl silicate or a partially hydrolyzed condensate thereof.