JP3369276B2 - Room temperature curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful room temperature curable resin composition. More specifically, the present invention provides a specific vinyl polymer having a tertiary amino group, an active hydrogen atom reactive with an isocyanate group, an epoxy group in one molecule, and an active isocyanate group. It is possible to give a cured product excellent in weather resistance and flexibility, in particular, by using a specific vinyl polymer having both a vinyl group and a hydrolyzable silyl group as an essential film forming component. ,
In particular, the present invention relates to a room temperature curable resin composition that is useful for paints, adhesives, sealing agents and the like.

[0002]

2. Description of the Related Art Hitherto, a vinyl polymer having a basic nitrogen atom has been used as a base resin component, while a curing agent has both an epoxy group and a hydrolyzable silyl group in one molecule. A composition in which the compound having the above is compounded is already known, and in addition, such a composition can be easily cured at room temperature to give a cured product having excellent weather resistance. It is also known. (JP-A-61-6074
No. 8 and 61-225244)

However, although the cured coating film obtained by such a method has high hardness, on the other hand, it tends to be very brittle, and therefore its use is limited.

Separately, a polymer having a hydroxyl group is mixed with a polyisocyanate compound,
The so-called urethane-curable resin composition is widely used as a material for imparting good flexibility, and is widely used for coating applications, but in particular, various properties such as weather resistance and stain resistance of the coating film are The reality is that it is far behind the conventional technology.

[0005]

However, the present inventor understands the present situation, and in view of the various problems in the prior art as described above, in particular, the weather resistance and stain resistance of the coating film are particularly high. In order to provide a novel, highly practical, room temperature curable resin composition with improved various properties such as the above, we have earnestly started research.

[0006] Therefore, the problem to be solved by the present invention depends on one and in particular, it is possible to give a cured product excellent in weather resistance and flexibility, which is novel and extremely practical. It is to provide a room temperature curable resin composition.

[0007]

Therefore, the present inventor has solved various problems in the prior art as described above,
At the same time, as a result of earnest and repeated studies so as to match the current situation, a tertiary amino group, an isocyanate group, and a group having an active hydrogen atom reactive (active hydrogen containing group) were combined. When a vinyl polymer having a vinyl polymer having both an epoxy group, an active isocyanate group and a hydrolyzable silyl group in a molecule as a curing agent is blended, it has excellent weather resistance. Of course, the present invention has been completed by finding that a curable resin composition excellent in flexibility and the like can be obtained.

That is, the present invention basically comprises, as essential components, a tertiary amino group and a group having an active hydrogen atom reactive with an isocyanate group (active hydrogen-containing group), respectively. And a vinyl polymer (A) having at least one epoxy group and at least one active isocyanate group in one molecule, and at least one hydrolyzable silyl group. The present invention is intended to provide a room temperature curable resin composition having an extremely high practicality, which comprises the combination (B).

The structure of the present invention will be described in detail below.

Here, first, the vinyl polymer (A) having both the above-mentioned tertiary amino group and a group having an active hydrogen atom reactive with an isocyanate group (active hydrogen-containing group) is used. A vinyl-based polymer having at least one, preferably two or more tertiary amino groups and groups having an active hydrogen atom reactive with an isocyanate group in one molecule. ,

The vinyl polymer (A) is a vinyl monomer containing a tertiary amino group according to claim 2 (hereinafter, also referred to as a vinyl monomer (a-1). ] And a vinyl-based monomer having a group having an active hydrogen atom (active hydrogen-containing group) [hereinafter, also referred to as a vinyl-based monomer (a-2). ]
And can be prepared by (co) polymerization by a conventional method.

Only typical examples of the above-mentioned tertiary amino group-containing vinyl monomer (a-1) used for preparing the vinyl polymer (A) are shown below. Then, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Such as dimethylaminopropyl (meth) acrylate or diethylaminopropyl (meth) acrylate,
Various dialkylaminoalkyl (meth) acrylates;

Various N-dialkylaminoalkyl such as N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide or N-diethylaminopropyl (meth) acrylamide. (Meth) acrylamides;

Alternatively, tert-butylaminoethyl (meth) acrylate, tert-butylaminopropyl (meth) acrylate, aziridinylethyl (meth)
Acrylate, pyrrolidinylethyl (meth) acrylate or piperidinylethyl (meth) acrylate,

From the viewpoint of curability, the use of dialkylaminoalkyl (meth) acrylates and N-dialkylaminoalkyl (meth) acrylamides is particularly desirable.

Further, a group having an active hydrogen atom reactive with an isocyanate group, which is copolymerizable with the above-mentioned vinyl monomer (a-1) containing a tertiary amino group (active hydrogen). Specific examples of the vinyl-based monomer (a-2) having a containing group) are 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Various (meth) acrylic acid esters having a hydroxyl group such as 4-hydroxybutyl (meth) acrylate;

(Meth) acrylic acid ester having a hydroxyl group at the side chain terminal obtained by ring-opening addition of a lactone such as ε-caprolactone to the above-mentioned hydroxyl group-containing (meth) acrylic acid ester; or (meth) They are unsaturated fatty acids such as acrylic acid, maleic acid and fumaric acid, and their monoalkyl esters.

In preparing the vinyl polymer (A), each of the vinyl monomers (a-
Of course, vinyl-based monomers other than 1) and (a-2) can also be used.

Of these, only typical ones are exemplified by methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate,
n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate Various (meth) acrylic acid esters such as:

Dimethyl malate, dimethyl fumarate,
Dialkyl esters of various unsaturated dibasic acids such as dibutyl fumarate or dimethyl itaconate; various acid anhydride group-containing vinyl monomers such as maleic anhydride or itaconic anhydride; p-styrene sulfonamide, Vinyl monomers containing various sulfonamide groups, such as N-methyl-p-styrenesulfonamide or N, N-dimethyl-p-styrenesulfonamide;

Various cyano group-containing vinyl monomers such as (meth) acrylonitrile; hydroxyalkyl esters of (meth) acrylic acid and hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, and phosphoric acid Or a vinyl monomer containing a phosphoric acid ester bond, which is a condensation product with a phosphoric acid ester; various vinylic monomers containing a sulfonic acid group such as p-styrenesulfonic acid or 2-acrylamido-2-methyl-propanesulfonic acid. body;

Various vinyl esters such as vinyl acetate, vinyl benzoate or "Veoba" (vinyl ester manufactured by Ciel Co., Netherlands); "Viscoat 8F, 8"
FM, 3F or 3FM "[fluorine-containing (meth) acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.] or perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or N-is.
o various (per) fluoroalkyl group-containing vinyl monomers such as propyl perfluorooctane sulfonamide ethyl (meth) acrylate;

Various halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride or chlorotrifluoroethylene; or styrene, α-methylstyrene, p-tert-butylstyrene or vinyltoluene. , Various aromatic vinyl monomers, and the like.

The composition of the present invention, which is an essential component, has at least one epoxy group and one or more active isocyanate group in each molecule, and also has one hydrolyzable silyl group.
The above vinyl-based polymer (B) having at least one of
These vinyl-based monomers having various functional groups are copolymerized, or if necessary, other vinyl-based monomers that can be copolymerized with these various vinyl-based monomers are also copolymerized. By doing so, it can be easily prepared.

Typical vinyl-based monomers, which can be used in this case, will be exemplified below.

First of all, only typical examples of vinyl monomers having one or more epoxy groups in one molecule will be given. Glycidyl acrylate, glycidyl methacrylate, β -Methylglycidyl acryl-
And various glycidyl group-containing (meth) acrylic acid esters such as β-methylglycidyl methacrylate,

Further, only typical vinyl monomers having one or more active isocyanate groups in one molecule will be exemplified, and the following general formula will be used. And a compound having such a structure.

[0028]

[Chemical 6]

[Wherein R ₁ is a hydrogen atom or a methyl group, and R ₂ is as follows:

[0030]

[Chemical 7]

[0031]

[Chemical 8]

Or

[0033]

[Chemical 9]

It represents a divalent bond as shown by: Further, n is a natural number of 1 to 12. ]

Among them, isocyanatoethyl (meth) is particularly preferable.
Examples thereof include various vinyl-based monomers such as acrylate or isocyanatopropyl (meth) acrylate.

Further, only the typical vinyl monomers having one or more hydrolyzable silyl groups in one molecule will be exemplified, and the following general formula will be given. If it is a vinyl-based monomer having a group
Either can be used.

[0037]

[Chemical 10]

[Wherein R ₁ is a hydrogen atom or a monovalent organic group consisting of an alkyl group, an aryl group or an aralkyl group, and R ₂ is a halogen atom or an alkoxyl group, an acyloxy group, a phenoxy group, an iminooxy group or It represents an alkenyloxy group, and a represents 0 or an integer of 1 or 2. ]

Of these, only typical ones are exemplified by vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, vinyltris (β).
-Methoxyethoxy) silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether or trimethoxysilylpropyl vinyl ether, etc.,

Or triethoxysilylpropyl vinyl ether, methyldiethoxysilylpropyl vinyl ether, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane or γ- (meth) acryloyloxypropylmethyl Examples include various hydrolyzable silyl group-containing monomers such as dimethoxysilane.

In order to prepare the vinyl polymer (A) using the various monomers listed above, the tertiary amino group-containing vinyl monomer (a- 0.5 to 90% by weight of 1), preferably 1 to 60% by weight,
Vinyl-based monomer (a-) having a group having an active hydrogen atom reactive with an isocyanate group (active hydrogen-containing group)
2) O. 5 to 50% by weight, preferably 1 to 30% by weight, and 99 to 0% by weight of other vinyl-based monomers copolymerizable with each of these vinyl-based monomers, preferably,
It may be copolymerized with 98 to 60% by weight.

Furthermore, in order to prepare the vinyl polymer (B) using the various monomers listed above, the epoxy group-containing vinyl monomer (b-1) is used. 1 to
90% by weight, preferably 5 to 60% by weight, and 1 to 90% of the vinyl monomer (b-2) containing an active isocyanate group.
% By weight, preferably 5 to 60% by weight, 1 to 90% by weight of the hydrolyzable silyl group-containing vinyl monomer (b-3), preferably 5 to 60% by weight, and It is advisable to copolymerize 97 to 0% by weight, preferably 85 to 0% by weight, of other vinyl-based monomers copolymerizable with various vinyl-based monomers.

In order to prepare the vinyl polymer (A) from the various monomers listed above, any known conventional polymerization method can be applied, of course, by the solution radical polymerization method. This is the most convenient and is recommended.

As the solvents to be used at that time, only representative ones are exemplified, and various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane and octane; methanol, ethanol, is
various alcohols such as o-propanol, n-butanol, iso-butanol, sec-butanol, ethylene glycol monomethyl ether;

Alternatively, various ester systems such as methyl acetate, ethyl acetate, -n-butyl acetate, amyl acetate;
Alternatively, there are various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and these solvents may be used alone or in combination of two or more.

A polymerization reaction may be carried out by a conventional method using such a solvent and various known and commonly used radical polymerization initiators such as azo-based or peroxide-based ones. If necessary, as a molecular weight regulator, lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α
Various chain transfer agents such as methyl styrene dimer can also be used.

The room temperature curable resin composition of the present invention does not necessarily require the addition of a curing catalyst, and therefore has good curability even if no such curing catalyst is added. However, if it is necessary to further improve this curability,
It does not preclude the addition of catalysts for the hydrolysis and condensation of the hydrolyzable silyl groups.

As only specific examples of the catalysts, various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide or sodium methylate; tetraisopropyl titanate, Tetra n-butyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di various metal-containing compounds such as n-butyltin dilaurate or di-n-butyltin maleate; or p-toluenesulfonic acid, trichloroacetic acid,
It is various acidic compounds such as phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid or dialkylphosphorous acid.

Most of these catalysts are active having reactivity with an isocyanate group. It promotes the reaction with hydrogen atoms.

In addition to the above, it goes without saying that in the present invention, a compound having a hydrolyzable silyl group may be used if necessary.

To exemplify only typical compounds of this type, "ethyl silicate 4
0 "(product of Corcort Co., USA), various ethyl ethyl silicate derivatives such as tetraethyl silicate, isopropyl silicate derivatives, methyl silicate derivatives, and the like; γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriisopropenyloxysilane, γ-glycidoxypropyltriiminooxysilane, γ-isocyanatopropyltriisopropenyloxysilane, γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and the like.

In order to prepare the room temperature curable resin composition of the present invention from both the essential components (A) and (B) as described above, the component (A) is used. Let p be the number of moles of tertiary amino groups present in the
Let q be the number of moles of a group having an active hydrogen atom reactive with an isocyanate (active hydrogen-containing group).

Further, when the number of moles of the epoxy group present in the component (B) is r and the number of moles of the active isocyanate group is s, (p + q) / (r
+ S) may be blended within a range such that the ratio becomes 1 / 0.2 to 5, preferably within a range from 0.5 to 2.

The room temperature curable resin composition of the present invention thus obtained may further contain, if necessary, organic or inorganic pigments, a flow control agent, a color separation preventing agent, an ultraviolet absorber or Various known and conventional additives such as antioxidants;

Alternatively, various kinds of fibrin derivatives such as nitrocellulose or cellulose acetate butyrate; further, various kinds of resins such as chlorinated polyethylene, chlorinated polypropylene, petroleum resin or chlorinated rubber may be added. I can.

The composition of the present invention can also be used as a solvent-free composition or can be used as a so-called solvent type composition in which solvents are added. is there.

The room-temperature-curable resin composition of the present invention thus obtained is applied onto various kinds of substrates to be coated by a conventional method, and then dried for several days according to a conventional method. Above all, it is possible to give a cured product excellent in weather resistance, flexibility and stain resistance.

The room temperature curable resin composition of the present invention is
In addition to automotive repair, woodworking, construction, building materials, glass, various plastic products, etc., it can also be used as a paint for various metal materials such as aluminum, stainless steel, chrome plating, etc. It can also be widely used as a sealing agent or an adhesive.

[0059]

EXAMPLES Next, the present invention will be explained more concretely by reference examples, examples and comparative examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 [Preparation example of vinyl polymer (A) having both tertiary amino group and hydroxyl group]

A reactor equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet was charged with 700 parts of toluene and 300 parts of n-butyl acetate and heated to 80 ° C. under a nitrogen atmosphere. 80 of methyl methacrylate
0 part, 100 of diethylaminoethyl methacrylate
Parts, 100 parts of 2-hydroxyethyl methacrylate,
A mixture consisting of 8 parts of azobisisobutyronitrile and 5 parts of tert-butylperoxyoctocate (TBPO) was added dropwise over 4 hours.

After the dropping, the temperature is kept at the same temperature for 10 hours, the nonvolatile content is 50%, and the amine value is 18 (m).
gKOH / g solution) with a hydroxyl value of 21 (mgKOH / g
g solution), and a target vinyl polymer (A) solution having a number average molecular weight of 9,000 was obtained. Hereinafter, this is abbreviated as a polymer (A-1).

Reference Example 2 (same as above) In the same manner as in Reference Example 1, a desired vinyl polymer (A) was obtained with a monomer composition as shown in Table 1. Hereinafter, this is abbreviated as a polymer (A-2).

Reference Example 3 [Preparation example of compound (B) having both epoxy group, active isocyanate group and hydrolyzable silyl group in one molecule]

A reaction vessel similar to that of Reference Example 1 was charged with 500 parts of xylene and heated to 140 ° C. in a nitrogen stream to obtain 630 parts of 2-ethylhexyl acrylate, 308 parts of glycidyl methacrylate, and isocyanate. 392 parts of triethylmethacrylate and 70 parts of γ-methacryloyloxypropyltrimethoxysilane,

140 parts of TBPO and 100 parts of xylene
The mixture consisting of 1 part and 6 parts was added dropwise over 6 hours, and the temperature was kept at the same temperature for 10 hours after the completion of the addition, the nonvolatile content was 70%, the epoxy equivalent was 920, and the NCO% was 5.
A solution of the desired compound of 3 was obtained. Hereinafter, this is abbreviated as (B-1).

Reference Example 4 (same as above) In the same manner as in Reference Example 3, a solution of the desired compound was obtained with the composition shown in Table 1. Hereafter, this is (B
-2) is abbreviated.

Reference Example 5 (Preparation Example of Control Resin) The control resin (A) was prepared in the same manner as in Reference Examples 1 to 4 except that the composition was changed as shown in Table 1. '-1) and (B'-1) were obtained.

Examples 1 and 2 and Comparative Examples 1 to 4 Various white paints having a pigment weight concentration (PWC) of 35% were prepared at the compounding ratios shown in Table 2.

Next, each of the coating materials was diluted to a spray viscosity with a mixed solvent of xylene / n-butyl acetate = 70/30 (volume ratio), and then applied on a zinc phosphate-treated steel plate and a tin plate. Each was spray-coated so that the dry film thickness was about 60 microns (μm), and then dried at room temperature for 7 days to obtain various cured coating films.

Regarding each of the cured coating films, the coating film applied on the tin plate was isolated from the substrate by the amalgam method and the elongation was measured, while the zinc phosphate-treated steel plate was treated. The coating film painted on the surface was exposed to the outdoors for 2 years in the suburbs of Miyazaki City, and the weather resistance was evaluated.

The results are shown together in the same table.

[0073]

[Table 1]

<< Footnote in Table 1 >> All the numerical values showing the amounts of the raw material monomers used are parts by weight.

(1) Styrene (2) Methyl methacrylate (3) n-Butyl methacrylate (4) 2-Ethylhexyl acrylate (5) Dimethylaminoethyl methacrylate (6) Diethylaminoethyl methacrylate (7) 2-Hydroxyethyl methacrylate (8) 4-Hydroxybutyl acrylate (9) Glycidyl methacrylate (10) Isocyanate Ethyl methacrylate (11) 2-Isocyanate acyl propylene (12) γ-methacryloxypropyl trimethoxysilane

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5]

<< Footnotes in Table 2 >> All the numerical values showing the mixing ratio of each component are parts by weight.

Γ-GPTMS .... Abbreviation for γ-glycidoxypropyltrimethoxysilane

1) Di-n-butyltin dioctate 2) Rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd. 3) The elongation is calculated from the following equation.
The larger this value, the better the flexibility.

[0083]

(However, L ₁ in the formula represents the length between chucks when the coating film is broken in the tensile test, while L ₀ is the distance between chucks when the sample is set before the tensile test. , That is, the length of the initial sample.)

4) "Weather resistance" is indicated by the gloss retention rate (%) based on the 60-degree specular reflectance, and the gloss retention rate is obtained from the following formula, and this value is large. The higher the value, the better the weather resistance.

[0086]

(In the formula, G ₁ represents the gloss value after 2 years of exposure, and G ₀ represents the initial gloss value.)

[0088]

[Table 6]

[0089]

[Table 7]

[0090]

EFFECTS OF THE INVENTION The room temperature curable resin composition of the present invention is, as shown in Examples 1 and 2 and Comparative Examples 1 to 4, particularly excellent in flexibility and weather resistance. It can be seen that it also gives a coating film of extremely high practicality.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C09D 5/00-201/10

Claims (3)

(57) [Claims] 1. A tertiary amino group as an essential component,
A vinyl polymer (A) having both an isocyanate group and a group having an active hydrogen atom that is reactive, and an epoxy group and an active isocyanate group in one molecule
A room temperature curable resin composition, which comprises at least one vinyl polymer (B) having at least one hydrolyzable silyl group. 2. The vinyl polymer (A) is selected from the group consisting of dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, N-dialkylaminoalkylacrylamide and N-dialkylaminoalkylmethacrylamide. The room temperature curable resin composition according to claim 1, which is obtained by copolymerizing at least one selected tertiary amino group-containing vinyl monomer. 3. The vinyl polymer (B) is glycidyl acrylate, glycidyl methacrylate, β-
At least 1 selected from the group consisting of methyl glycidyl acrylate and β-methyl glycidyl methacrylate.
Kind of vinyl-based monomer, active-isocyanate group-containing vinyl-based monomer represented by the following general formula (1), and hydrolysis represented by the following general formula (2) The room temperature curable resin composition according to claim 1, which is obtained by copolymerizing a vinyl silyl group-containing vinyl monomer as an essential raw material component. [Chemical 1] [Wherein R ₁ represents a hydrogen atom or a methyl group,
R ₂ is as follows: [Chemical 3] Or [Chemical 4] Represents a divalent bond. Further, n is a natural number of 1 to 12. ] [Chemical 5] [Wherein R ₁ is a hydrogen atom or an alkyl group,
A monovalent organic group consisting of an aryl group or an aralkyl group,
R ₂ represents a halogen atom, an alkoxyl group, an acyloxy group, a phenoxy group, an iminooxy group or an alkenyloxy group, and a represents 0 or an integer of 1 or 2. ]