JP2003012804A - Solvent-free liquid type curable resin composition and paint composition for forming cured coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substantially solvent-free liquid type curable resin composition which can achieve relatively high surface hardness from the beginning of curing without causing the problems such as odors and environmental pollutions and impairing the characteristics such as excellent surface hardness, heat resistance, weatherability chemical resistance which an inorganic curable composition having a siloxane bond as a skeleton has and which is excellent in thick coating properties, high concentration organic acids resistance or the like without having a problem of the cracking development after curing and further has a room temperature-curing property. SOLUTION: The solvent-free liquid type curable resin composition is characterized by having a specific recurring unit A of vinyl polymerization represented by the formula (1) and/or the formula (2) and a specific recurring unit B of siloxane bond represented by the formula (3) in the same molecule or different molecules and being substantially solvent-free liquid at normal temperatures under atmospheric pressure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel solventless liquid type curable resin composition which gives a cured film excellent in surface hardness, chemical resistance, weather resistance and stain resistance. The present invention relates to a coating composition for forming a cured film obtained by using the composition.

[0002]

2. Description of the Related Art Conventionally, melamine-based coating compositions such as alkyd melamine and acrylic melamine have been used in the line coating of automobiles, steel furniture, building materials, etc. It has been pointed out that there is a problem of odor generated during baking and weather resistance, particularly that it is susceptible to acid rain.

In addition, the two-component acrylic urethane type coating composition which is generally used in the fields of construction, civil engineering, etc.
In addition to problems in using solvents, it has been pointed out that the polyisocyanate used as a curing agent has toxicity problems. In addition, it is a room temperature dry two-component fluororesin coating agent that is said to have the highest weather resistance. The composition has a problem that stains and scratches are likely to occur in the initial stage of curing.

Therefore, in order to solve these problems,
A thermosetting resin composition containing a resin having a hydroxyl group such as a polyol, an alkoxysilyl group-containing copolymer, and a curing catalyst has been proposed (JP-A-1-141952). However, in this thermosetting resin composition, there are problems that the water resistance and chemical resistance are not sufficient and the thermosetting resin composition is easily attacked by water and a solvent, and that heating at 55 to 350 ° C. is required for curing.

A curable composition prepared by blending a zirconium chelate compound with a copolymer of a vinyl monomer containing an alkoxysilyl group and a vinyl monomer containing an alicyclic epoxy group (see, for example, JP-A-63- No. 108,049) has been proposed, but the curable composition has a problem of poor weather resistance and low temperature curability.

By the way, in recent years, an inorganic curable composition using an organopolysiloxane having a siloxane bond as a basic skeleton has been proposed as a solution to various problems in the organic curable resin composition as described above. Proposed, surface hardness, heat resistance, weather resistance of the formed cured film,
Due to its excellent chemical resistance and other properties, it is beginning to be used not only in heat-resistant applications but also in the field of construction. However, unlike the organic curable resin composition, the curable composition using the organopolysiloxane has a brittle resistance, crack resistance, and
Its performance is inferior in terms of alkali resistance, shrinkage resistance, etc., and high temperature curing is required.

Most curable compositions, including curable compositions using this type of organopolysiloxane, generally contain a solvent in an amount of 50 to 70% by weight. When a film is formed, the film thickness is so thin that the problem of film defects easily occurs. On the other hand, there are solventless liquid type epoxy resins and urethane resins, but such solventless liquid type epoxy resins and urethane resins have weather resistance and discoloration due to their resin skeleton. sex,
There is a problem that the performance such as chemical resistance is poor and the place of use is limited due to this.

Furthermore, a solvent-free, one-liquid type room temperature-curable organopolysiloxane composition containing a liquid organopolysiloxane, a crosslinking agent composed of an organometallic compound, and a curing catalyst composed of a metal-containing compound as essential components (special Kaihei 5-2
47347). However, in this solventless one-liquid type room temperature curing type organopolysiloxane composition, a volatile monomer is used as a cross-linking agent, alcohol is used in order to delay and control the curing rate, and the like. It is hard to say that it is a solvent, and in curable compositions using this type of organopolysiloxane, the problem of cracking after curing during thick coating or contact with high-concentration organic acid, which is thought to be difficult to solve, is a problem. Is still left.

That is, regarding the curable compositions proposed so far, in the organic curable resin composition, the surface hardness, heat resistance, stain resistance, weather resistance and chemical resistance (acid resistance) , Alkali resistance, oxidant resistance), and has no room temperature curability and practically no solvent-free liquid type curable resin composition. In a conductive composition, it is excellent in thick coatability, high-concentration organic acid resistance, etc. and has no problem of crack generation after curing, and it has room temperature curability and is a substantially solventless liquid type curable resin. The composition has not been put to practical use.

[0010]

Therefore, the present inventors have made it a difficult problem to solve in this type of inorganic curable composition without impairing the features of the inorganic curable composition having a siloxane bond. There is no problem of crack generation after curing, and further, as a result of diligent study to develop a liquid type curable resin composition that has room temperature curability and is substantially solvent-free, the side chain is hydrolyzable. A curable resin composition having a repeating unit A of a vinyl polymerization having an alkoxysilyl group and a repeating unit B of a siloxane bond in the same molecule or in different molecules is substantially solvent-free and is liquid at room temperature and normal pressure, The present invention was completed by finding out that it has curability at room temperature.

Therefore, an object of the present invention is to achieve a relatively high surface hardness from the initial stage of curing without problems such as odor and environmental pollution, and an inorganic curable composition having a siloxane bond as a skeleton. The surface hardness, heat resistance, weather resistance, chemical resistance, etc. possessed by the above do not impair the characteristics, and they are also excellent in thick coatability, high-concentration organic acid resistance, etc. Another object of the present invention is to provide a curable resin composition that is curable at room temperature and has a substantially solvent-free liquid type.

[0012]

That is, the present invention provides the following general formula (1):

[0013]

[Chemical 7]

[Wherein, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and R ² represents -CO-O- (CH ₂ ) _x-
(However, x is an integer of 1 to 6),-(CH ₂ ) _x- (however,
x is an integer of 1 to 6), or a single bond between a carbon atom and a silicon atom, R ³ is an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, Three R
^At least one of ³ is an alkoxy group] and / or the following general formula (2)

[0015]

[Chemical 8]

[Wherein, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and R ² represents -CO-O- (CH ₂ ) _x-
(However, x is an integer of 1 to 6),-(CH ₂ ) _x- (however,
x is an integer of 1 to 6), or a single bond between a carbon atom and a silicon atom, R ³ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and silicon A single bond from an atom is bonded to an oxygen atom of a siloxane bond] and a repeating unit A of vinyl polymerization represented by the following general formula (3)

[0017]

[Chemical 9]

(In the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, an alkenyl group, an aryl group, a hydroxyl group, and a hydrogen atom. , Which may be the same or different from each other) in the same molecule or in different molecules, and which is substantially solvent-free and liquid at room temperature and normal pressure. It is a solventless liquid type curable resin composition characterized by being present.

In the present invention, the repeating unit A of vinyl polymerization having a hydrolyzable alkoxysilyl group in the side chain represented by the general formula (1) is a vinyl-based monomer having a hydrolyzable alkoxysilyl group in the molecule. Formed by polymerization of the body, specifically, a homopolymerization of this vinyl monomer or a monomer copolymerizable with this vinyl monomer (hereinafter referred to as "copolymerizable monomer") Formed by copolymerization with. Hereinafter, the polymer having the repeating unit A of vinyl polymerization represented by the general formula (1) is referred to as a "vinyl-based (co) polymer".
Say.

The vinyl monomer having a hydrolyzable alkoxysilyl group in the molecule is not particularly limited as long as it is a compound having a polymerizable vinyl group and a hydrolyzable alkoxysilyl group in the molecule. For example, the following can be exemplified as suitable ones, and these vinyl-based monomers can be used alone or in combination of two or more kinds.

CH ₂ = CH-Si (OCH ₃ ) ₃ , CH ₂ = CH-Si (OC ₂ H ₅ ) ₃ , C
_{H 2 = CH-Si (CH} 3) (OCH 3) 2, CH 2 = CH-Si (CH 3) (OC 2 H 5) 2, CH 2 =
_{CH-Si (OC 2 H 4} OCH 3) 3, CH 2 = CH-Si [OCH (CH 3) 2] 3, CH 2 = CH-S
i (OCOCH ₃ ) ₃ , CH ₂ = CHCOO (CH ₂ ) ₃ -Si (OCH ₃ ) ₃ , CH ₂ = CHCOO (C
_{H 2) 3 -Si (CH 3} ) (OCH 3) 2, CH 2 = CHCOO (CH 2) 3 -Si (OC 2 H 5) 3, C
_{H 2 = CHCOO (CH 2)} 3 -Si (CH 3) (OC 2 H 5) 2, CH 2 = C (CH 3) COO (CH 2)
_{3 -Si (OCH 3) 3,} CH 2 = C (CH 3) COO (CH 2) 3 -Si (CH 3) (OCH 3) 2, C
_{H 2 = C (CH 3)} COO (CH 2) 3 -Si (OC 2 H 5) 3, CH 2 = C (CH 3) COO (CH 2) 3
_{-Si (CH 3) (OC 2} H 5) 2

The copolymerizable monomer copolymerizable with the vinyl monomer is not particularly limited as long as it is copolymerizable with the vinyl monomer. For example, methyl ( (Meth) acrylate, ethyl (meth) acrylate, etc. (meth) acrylic acid esters such as C ₁ -C ₁₈ alkyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, Functional group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, and fluorine-containing (meth) groups such as trifluoroethyl (meth) acrylate and pentafluoropropyl (meth) acrylate.
Acrylates, nitriles such as (meth) acrylonitrile, (meth) acrylamines such as (meth) acrylamide, α-ethyl (meth) acrylamide, and further (meth) acrylic acid, maleic anhydride, etc. Examples thereof include unsaturated carboxylic acids and anhydrides thereof, and also polymerizable monomers such as styrene and derivatives thereof, vinyl esters and vinyl ethers.

When the vinyl monomer and the copolymerizable monomer are copolymerized, the proportion of the vinyl monomer used is usually 0. 5-80
mol%, preferably 5-40 mol%, more preferably 10
It is preferably in the range of ˜20 mol%. When the use ratio of this vinyl-based monomer is less than the above range, the resulting cured film tends to become turbid, and conversely, when it is more than the above range, the cause of gelation during synthesis, and during curing Cause contraction.

Regarding the polymerization method for homopolymerizing the vinyl monomer or copolymerizing the vinyl monomer and the copolymerizable monomer, the homopolymerization or copolymerization [hereinafter,
There is no particular limitation as long as "(co) polymerization"] is possible, but preferably 2,2'-azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis as a polymerization initiator. Azo initiators such as isobutyronitrile and 2,2'-azobis (2-methylbutyronitrile), and organic peroxides such as t-butylperoxypivalate, benzoylperoxide and t-butylperoxybenzoate The radical solution polymerization may be carried out using a physical initiator in the presence of a non-ester solvent having a boiling point of 140 ° C. or lower under normal pressure or reduced pressure. Like this
By using a low boiling point organic solvent that does not substantially contain water as a solvent for the polymerization reaction, it is possible to prevent gelation during (co) polymerization, as well as the subsequent hydrolysis step and the final removal of the solvent. The process can be carried out advantageously.

In the present invention, the repeating unit A of the vinyl polymerization represented by the general formula (2) is the vinyl-based (co) polymer, an alkoxysilane monomer, and a part of the alkoxysilane monomer. One or two selected from a hydrolyzed condensate and a vinyl-based (co) polymer having a repeating unit A of vinyl polymerization having a hydrolyzable alkoxysilyl group in the side chain represented by the general formula (1). It is a repeating unit obtained by condensing one or more species, and the repeating unit B having a siloxane bond represented by the general formula (3) is obtained by condensing an alkoxysilane monomer and / or a partial hydrolysis-condensation product thereof. It is a repeating unit obtained by

The solventless liquid type curable resin composition of the present invention is a vinyl polymerization represented by the above general formula (1) and / or general formula (2) in the same molecule or in different molecules. Is a repeating unit A and a repeating unit B having a siloxane bond represented by the general formula (3), and is preferably produced by the following method.

First, the first method is the following general formula (4) in the presence of a vinyl (co) polymer having a hydrolyzable alkoxysilyl group in the side chain.

[0028]

[Chemical 10]

(In the formula, R ⁴ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, hydroxyl group, and
It is a substituent selected from the group consisting of a substituted or unsubstituted alkoxy group, which may be the same or different from each other, and at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups. ) Is a method of hydrolyzing and condensing an alkoxysilane monomer represented by) or a partial hydrolyzed condensate thereof.

In the second method, first of all, a vinyl (co) polymer having a hydrolyzable alkoxysilyl group in its side chain is used.
In the presence of a part of the polymer, the alkoxysilane monomer represented by the general formula (4) or a partial hydrolysis-condensation product thereof is hydrolyzed and condensed to produce a resin mixture, and then the obtained resin mixture is added. It is a method of preparing by mixing the rest of the vinyl-based (co) polymer.

Furthermore, as a third method, the curable resin composition obtained by the above-mentioned first method is used as a reactive compatibilizer, and a vinyl type (co) having a hydrolyzable alkoxysilyl group in its side chain is used. This is a method in which a polymer and an organopolysiloxane obtained by subjecting an alkoxysilane monomer represented by the general formula (4) or a partial hydrolysis-condensation product thereof to hydrolysis-condensation are mixed at a predetermined ratio. .

Further, as a fourth method, the curable resin composition obtained by the first method and the alkoxysilane monomer represented by the general formula (4) or a partial hydrolysis-condensation product thereof are hydrolyzed. This is a method in which an organopolysiloxane obtained by decomposition and condensation is mixed at a predetermined ratio to prepare.

Here, the alkoxysilane monomer represented by the above general formula (4) is not particularly limited, and typical examples thereof include tetramethoxysilane, tetraethoxysilane, methyldimethoxysilane, Triethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltris (2-methoxyethoxy) silane and the like, reactivity, From the viewpoint of compatibility, chemical resistance, etc., methyltrimethoxysilane or phenyltrimethoxysilane is preferable. These alkoxysilane monomers may be used alone, or 2
You may mix and use 1 or more types.

The alkoxysilane monomer or its partial hydrolysis-condensation product is hydrolyzed in the presence of a part or all of the vinyl-based (co) polymer or in the absence of the vinyl-based (co) polymer. In the hydrolysis-condensation reaction in which the repeating unit B of the siloxane bond is formed by decomposition and condensation, the solvent used is not particularly limited as long as it is a non-reactive solvent, and examples thereof include alcohols such as methanol, ethanol and propanol, and ethylene. Examples thereof include alkylene glycols such as glycol and propylene glycol monomethyl ether, hydrocarbons such as toluene, xylene and n-hexane, and ketones such as MEK and MIBK. Considering the solvent step, it is a non-ester solvent having a boiling point of 140 ° C. or lower under normal pressure or reduced pressure. The boiling point of the solvent used is 1 under normal pressure or reduced pressure.
If it exceeds 40 ° C, the repeating unit A of vinyl polymerization may cause depolymerization in the desolvation step, and when an ester solvent is used, the ester bond of this solvent is hydrolyzed during the hydrolysis condensation reaction. Therefore, the added water is consumed, the hydrolysis of the alkoxysilane monomer becomes insufficient, and there is a possibility of causing a problem that the molecular weight decreases. At this time, the type of the alcohol produced by hydrolysis and the type of the solvent to be used are selected in consideration of the solvent recovery and reuse afterwards, so that the hydrolysis-condensation reaction is carried out more efficiently industrially. be able to.

The amount of water added for the hydrolysis condensation reaction is not particularly limited, but is 0.3 to 5.0 times the total number of moles of the alkoxysilane monomer, preferably 0. 6 to 3.0 times mol, more preferably 0.8 to
It is preferable to select it in the range of 1.5 times mol. When the amount of water added exceeds 5.0 times the theoretical amount, gelation occurs, or the curable resin composition obtained does not become liquid at room temperature and normal pressure. Theoretical 0.3
If the amount is less than twice the molar amount, a relatively large amount of the monomer remains and the shrinkage during film formation becomes large, which causes cracks.

Further, a catalyst may be added to the reaction system in order to accelerate the hydrolysis condensation reaction. Examples of the catalyst include inorganic / organic acids such as hydrochloric acid, phosphoric acid, phosphoric acid ester, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid and oxalic acid, and solid catalysts such as ion exchange resins (Amberlite manufactured by Organo Co., etc.). ), Organometallic compounds (Al alkoxides, Al chelate compounds, Zr chelate compounds, Ti chelate compounds, etc.) and the like.

Further, the size (molecular weight) of the repeating unit B of the siloxane bond is arbitrarily adjusted by adjusting the kind and blending amount of the catalyst used, the blending amount of water to be added, the reaction time, the reaction temperature and the like. be able to. Then, the reaction solvent or alcohol of the reaction by-product used in this hydrolysis condensation reaction is used as a reaction product under normal pressure or reduced pressure.
It can be easily separated and removed by heating to a temperature of ℃ or less, preferably 110 to 135 ℃.

Here, in the solventless liquid type curable resin composition of the present invention, the ratio of the repeating unit A of vinyl polymerization and the repeating unit B of siloxane bond is usually 0.5 to 50% by weight. %, Preferably 5-30% by weight,
It is more preferably 10 to 20% by weight, and the repeating unit B is 99.5 to 50% by weight, preferably 95 to 70% by weight, more preferably 90 to 80% by weight.
When the abundance ratio of the repeating unit A exceeds 50% by weight,
The viscosity of the curable resin composition increases and it becomes impossible to maintain the liquid form, and it becomes difficult to form a polysiloxane matrix in the resulting cured film. On the contrary, when the content of the repeating unit A is less than 0.5% by weight, curability, alkali resistance and flexibility are poor, and it becomes difficult to suppress shrinkage cracks, thereby achieving the object of the present invention. Will not be able to get.

The solventless liquid type curable resin composition of the present invention, by itself, interpenetrates the organic skeleton and the inorganic skeleton by the hydrolytic condensation of the hydrolyzable alkoxysilyl groups present in the composition. Structure (Interpenetrating polymer n
etwork) and crosslinks at room temperature to cure, and has excellent surface hardness, heat resistance, weather resistance, chemical resistance, etc.
It has excellent properties such as thick coatability and high-concentration organic acid resistance, and has the property of forming a glass-like cured film that does not cause the problem of cracks after curing, and is widely used in construction, civil engineering, metal, plastic, etc. Can be used.

In order to use the solventless liquid type curable resin composition of the present invention as a coating composition for forming a cured film, it is preferable to use the hydrolyzable alkoxysilyl group in the curable resin composition. A condensation catalyst (curing catalyst) is added in order to accelerate the hydrolysis-condensation reaction (that is, the curing reaction).

The condensation catalyst used for this purpose includes
For example, tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bistriethoxysilicate and other organotin compounds, titanium, zirconium and other organometallic alcoholates or organometallic chelates, phosphoric acid or phosphate esters, acidic phosphate esters. Reaction products of amines with amines, addition products of epoxy compounds with phosphoric acid and mono-acidic phosphoric acid esters, carboxylates of organic amines, various alkali metal hydroxides, alkali metal carbonates, alkali metal alcoholates, various onium salts, phosphines, Examples include amines, amidines, and guanidines. The amount of these condensation catalysts used is usually 0.01 to 5% by weight, preferably 0.0
It is in the range of 5 to 3% by weight, and if it is less than 0.01% by weight, the curability may not be sufficiently exerted, which may cause curing failure. Conversely, if it is added in excess of 5% by weight, it can be remarkably used. It is not realistic because it shortens the time.

The solvent-free liquid type curable resin composition of the present invention has a property of forming a glass-like cured film free from the problem of cracking after curing by itself cross-linking and curing. Depending on the pigment, UV absorber, water repellent,
Additives such as an anti-settling agent and a leveling agent, a fiber resin such as cellulose acetate butyrate, and a third component such as a plasticizer can be added.

The solventless liquid type curable resin composition of the present invention and the coating composition for forming a cured film prepared by using the curable resin composition are applied by brush coating, spray coating, It is possible to adopt a commonly used method such as roll coating, and an appropriate method from room temperature curing to heat curing as its curing method, which has a wide range of applications in the fields of construction, civil engineering, metal, plastic, etc. Can be used for, and is not only excellent in surface hardness, heat resistance, weather resistance, chemical resistance, etc., but also excellent in thick coatability and high-concentration organic acid resistance. Gives no cured film.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be specifically described below based on Synthesis Examples, Examples and Comparative Examples.

Synthesis Examples 1 to 5 [Preparation of vinyl-based (co) polymer having repeating unit A] 1 equipped with a Teflon (registered trademark) -coated stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube A liter glass four-neck reaction vessel was charged with dehydrated methanol or toluene shown in Table 1 and heated to the reaction temperature shown in Table 1 while introducing dry nitrogen gas. Methyl methacrylate (MMA), n-butyl methacrylate (BMA), ethyl acrylate (EA), styrene (SM), n-butyl acrylate (BA), 2-acrylate
Ethylhexyl (2EHA), γ-methacryloxypropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. product name: KB
M502), γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name: KBM503), 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd. trade name: V- 65) and 2,2'-azobis (2-methylbutyronitrile) (trade name: V-59 manufactured by Wako Pure Chemical Industries, Ltd.), and a mixture of the components shown in Table 1 at a constant rate over 3 hours. After completion of the dropping, the mixture of the components shown in Table 1 selected from methanol, toluene, V-65, and V-59 was added dropwise while maintaining the reaction temperature shown in Table 1 for 2 hours, and then for 3 hours. The mixture was aged and cooled to obtain the vinyl (co) polymer of the present invention.

The properties of the obtained vinyl-based (co) polymer, the heating residue (according to JIS K5407), the viscosity (according to JIS K5400), and the number average molecular weight (GPC method) together with the raw material composition and the reaction temperature were measured. , Shown in Table 1.

[0047]

[Table 1]

Further, the vinyl-based (co) obtained in Synthesis Example 1
The results of measuring the molecular weight distribution, FT-IR, proton NMR, and dynamic viscoelasticity of the polymer are shown in FIGS.

Here, the molecular weight distribution was determined by using a high-speed GPC device (HLC-8120GPC manufactured by Tosoh Corporation) and using TSK as a column.
Gel SUPER HM-H x 2 + TSK gel SUPER H2000 x 1 is used, measurement temperature: 40 ° C, flow rate: 0.6 ml / min., solvent:
THF, sample concentration: 1%, Injection: 20 μl,
Calibration curve: Standard polystyrene calibration curve, differential refraction data (R
It was measured under the condition of I).

The FT-IR was measured by the KBr-thin film transmission method using an IR measuring device (FT / IR-300E manufactured by JASCO Corporation). Furthermore, regarding proton NMR,
Using an NMR measuring device (JNM-400 manufactured by JEOL Ltd.), temperature: room temperature, solvent: CDCl ₃ , sample concentration: 1.3
%, NMR tube: measured under the condition of 5 mm.

For dynamic viscoelasticity, a solid analyzer (RSA-II manufactured by Rheometric Scientific F.E.) was used, and a sample dried at room temperature for 7 days after being coated with a 20 mil applicator was used. Use, frequency: 1Hz, temperature range: -60 to 160
C., temperature rising rate: 5.degree. C./min, and STRAIN: 0.15%.

Synthesis Examples 6 to 11 [Preparation of Curable Resin Composition Having Repeating Units A and B] 1 liter glass equipped with a Teflon-coated stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube As shown in Table 2, the four-neck reaction vessel was charged with the vinyl-based (co) polymers obtained in Synthesis Examples 1 to 5 and methyltrimethoxysilane (MTMS) and phenyltrimethoxysilane (PTMS), The mixture was stirred at 35 ° C while introducing dry nitrogen gas until uniform.

Then, a mixture of 2 wt% dilute hydrochloric acid, distilled water, and methanol was added dropwise to the reaction vessel over 1 hour while maintaining the temperature at 40 ° C. or lower, and 30 minutes after the completion of the addition, the monomer was completely removed by gas chromatography. After confirming that the solid phenylalkyl type silicone intermediate (Toray Dow Corning Silicone Co., Ltd., product name: SH6018) was added to the reaction vessel to completely dissolve it, aluminum monoacetyl as a catalyst was further added. Acetoneate Bis (ethyl acetoacetate) in 76 wt% isopropyl alcohol solution (Kawaken Fine Products Co., Ltd .: Aluminum chelate D) was diluted with methanol and added, and the mixture was heated for 30 minutes and refluxed for 3 times. Reacted for hours. The boiling point at this time was 65 to 68 ° C.

Then, the reflux condenser was replaced with a dehydration condenser, the temperature was raised to 135 ° C., the solvent in the reaction system was distilled off over 2 hours, and then the mixture was cooled to give a pale yellow transparent viscous liquid. A curable resin composition which is a liquid was obtained. In the desolvation step, almost the theoretical amount of the solvent could be distilled off, and no volatile component was detected from the results of the gas chromatography analysis of the obtained curable resin composition.

The properties, volatile matter (GC method), viscosity (according to JIS K5400), and number average molecular weight (GPC method) of the obtained curable resin composition are shown in Table 2 together with the raw material composition. Also,
Molecular weight distribution of the curable resin composition obtained in Synthesis Example 6, F
The results of measuring T-IR, proton NMR, and dynamic viscoelasticity under the same conditions as above for coating are shown in FIGS.

Synthesis Example 12 [Preparation of Organopolysiloxane Having Repeating Unit B] In the same manner as in Synthesis Examples 6 to 11 except that the vinyl (co) polymer of Synthesis Examples 1 to 5 was not used. , An organopolysiloxane was synthesized. The properties, volatile matter (GC method), viscosity (according to JIS K5400), and number average molecular weight (GPC method) of the obtained curable resin composition are shown in Table 2 together with the raw material composition.

[0057]

[Table 2]

Examples 1-5 and Comparative Examples 1-6 Curable resin compositions having repeating units A and B obtained in Synthesis Examples 6-11, organopolysiloxane obtained in Synthesis Example 12, acrylic polyol ( Dainippon Ink and Chemicals, Inc. product name: Acridic A801), solventless liquid straight silicone resin (Toray Dow Corning Silicone product name: SR2402), solventless liquid straight silicone resin (Shin-Etsu Chemical Co., Ltd. product name: X40- 9225), dibutyltin diacetate (Nitto Kasei's trade name: Neostan U2
00) and polyisocyanate (trade name: Duranate THA100 manufactured by Asahi Kasei Co., Ltd.) are blended at the blending ratios shown in Table 3 and mixed until uniform, and Examples 1 to 5 and Comparative Example 1 are prepared.
A coating composition for forming a cured film of ~ 6 was prepared.

Example 6 The vinyl copolymer having the repeating unit A obtained in Synthesis Example 1 was subjected to an evaporator under the conditions of a temperature of 60 ° C. and a pressure of 70 cmHg, and the solvent (methanol) in this vinyl copolymer was distilled off. Then, the obtained solvent-removed product of Synthesis Example 1, the curable resin compositions of Synthesis Examples 6 and 12 and dibutyltin diacetate (Neostan U200) were blended at the blending ratios shown in Table 3 until uniform. A coating composition for forming a cured film of Example 6 was prepared by mixing.

The coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were applied on a bonderite steel plate using a 5 mil applicator and then dried and cured at room temperature for 7 days to give an appearance of the cured film. , Surface hardness (after 1 and 7 days),
Chemical resistance, long-term water resistance, high concentration organic acid resistance, thick coatability,
The dynamic viscoelasticity E ′ retention rate, weather resistance, and baking crack resistance were investigated, and the MIBK rubbing test and boiling test were performed. The test method of each performance test is as follows, and the results are shown in Table 3 together with the coating composition.

[Appearance] The appearance of the cured film is visually observed,
The evaluation was made in three grades: ◯: good, Δ: normal, and x: poor. [Surface Hardness] The surface hardness of the cured film was measured after 1 day and 7 days according to JIS K5400.

[Chemical resistance] 10 w of NaOH, H ₂ SO ₄ , and HNO ₃
A t% aqueous solution and a fungicide containing trichloroisocyanuric acid as the main component (Nissan Chemical Co., Ltd. product name: Highlight 90)
Saturated aqueous solution was prepared, several drops of these chemicals were spotted on the cured film, covered with a lid and left for 48 hours, after which the chemicals were wiped off and the traces after the wiping were examined, ○: no abnormality, △ It was evaluated in three levels: slightly spotted and slightly whitened spot marks, and x: completely glossed, whitening or blistering, swelling, or cracking.

[Long-term water resistance] A cured film dried and cured at room temperature for 7 days was immersed in distilled water for 7 days, and the traces after the water was wiped off were examined. It was evaluated in 3 stages: glossy, slightly whitened, and x: completely glossed, whitening or blistering, blistering, or cracking occurred.

[High-concentration organic acid resistance] A 50 wt% acetic acid aqueous solution is thoroughly soaked in absorbent cotton, the absorbent cotton is placed on a cured film, and the cover is covered with a lid and left for 24 hours. Wipe off and inspect the trace, ○: No abnormality,
(Triangle | delta): The spot mark is slightly glossed and a little whitening has occurred, and X: It is completely glossed, and whitening or blistering, blistering, or cracking has occurred.

[MIBK Rubbing Test] A new tissue paper was soaked with MIBK, and the surface of the cured film was rubbed 100 times back and forth with this tissue paper, and then the surface condition was observed. ○: no abnormality, △: scratches remained, And ×: causes softening or lifting, and sometimes dissolves,
It was evaluated in three stages.

[Thick coatability] A cured film applied with a 10 mil applicator was cured at 45 ° C. for 7 days, and then the surface condition of the cured film was observed. ○: No abnormality, Δ: Partially wrinkled, cracked , Cracking, and / or peeling, x: wrinkles, cracks, cracks, and / or
Or, the peeling occurred, and the evaluation was made in three stages.

[Dynamic viscoelasticity E'retention rate] Using a solid analyzer (RSA-II, manufactured by Rheometric Scientific FE),
Frequency 1Hz, temperature range -50 to 150 ° C (temperature range that can cover Tg), heating rate 5 ° C / min, STRAIN: 0.15
% Change the physical properties before and after the glass transition point (Tg) under the measurement conditions, and calculate the following formula E'-retention rate (%) = {(storage elastic modulus at 150 ° C) / (storage elasticity at -50 ° C) E'-retention rate (%) was calculated by the following equation.

[Weather Resistance] Weather resistance tester (UV manufactured by Atlas
CON UC-1 type), and after exposing for 1200 hours, visually observe the surface of the cured film, ○: no abnormality, △: gloss gloss,
The evaluation was made in 3 stages: stains such as water stains were observed, x: significant chalking and / or cracking occurred.

[Boiling test] For each coating composition of Examples 1, 2 and 6 and Comparative Examples 1, 2, 5 and 6, a bonderite steel plate having a cured coating on the surface was erected in a enamel container, and The container was filled with distilled water to half the height of the bonderite steel plate, covered with aluminum foil and boiled for 2 hours, then the bonderite steel plate was taken out and rapidly cooled to room temperature, and the hardened film on the surface was observed. There were no abnormalities, Δ: whitening, glossiness and the like remained partially, ×: whitening, glossiness, and / or cracks were generated on the entire surface of the immersed portion, and the evaluation was made in 3 grades.

[Baking Resistance to Cracking] The coating compositions of Examples 1, 2 and 6 and Comparative Examples 1, 2, 5 and 6 were applied on a bonderite steel sheet using a 5 mil applicator and dried at room temperature for 24 hours. After that, it is baked at 150 ° C. for 30 minutes and then rapidly cooled to room temperature. The state of the obtained cured film is ◯: no abnormality, Δ: some cracks and peeling are observed, ×: cracks on the entire surface The peeling was recognized, and the evaluation was made in three levels.

[0071]

[Table 3]

Examples 7-10 and Comparative Examples 7-9 Curable resin composition having repeating units A and B obtained in Synthesis Example 6 or 8, SR2402, solvent type phenylmethyl silicone resin (containing 40 wt% of toluene) (Toray Dow Corning Silicone product name: SH804), Neostan U200,
And epoxy toner (red rust color) (trade name: Base Color Brown 3C701, manufactured by Dainichi Seika Kogyo Co., Ltd.) in the proportions shown in Table 4, and mixed until uniform to give Examples 7-10 and Comparative Examples 7-9. A coating composition for forming a cured film was prepared.

The obtained Examples 7 to 10 and Comparative Examples 7 to 9
Of the coating composition of the present invention was applied on a bonderite steel plate using a 5 mil applicator and then baked at 150 ° C. for 30 minutes to cure, and the surface hardness of the obtained cured film, dynamic viscoelasticity E ′ retention rate, The weather resistance and baking crack resistance were examined, and the MIBK rubbing test and boiling test were performed. In the boiling test, the surface hardness of the cured film immediately after the test was measured. The surface hardness, the MIBK rubbing test, the dynamic viscoelasticity E ′ retention rate, the weather resistance, and the test method for each performance test of the boiling test are the same as those in Examples 1 to 6, and the results are shown in the coating composition. Are shown in Table 4.

[0074]

[Table 4]

[0075]

The solventless liquid type curable resin composition for forming a cured film of the present invention has no problems such as odor and environmental pollution, and can achieve a relatively high surface hardness from the initial stage of curing. Moreover, in addition to being excellent in surface hardness, heat resistance, weather resistance, chemical resistance, etc., it is also excellent in thick coatability and high-concentration organic acid resistance, so there is no problem of cracking after curing, various coating materials In particular, it is particularly useful as a coating composition that forms a cured film for acid resistance, heat resistance, hard coating and the like.

[Brief description of drawings]

FIG. 1 is a vinyl system (co) obtained in Synthesis Example 1.
It is a graph which shows the measurement result of the molecular weight distribution of a polymer.

FIG. 2 is a vinyl-based (co) polymer obtained in Synthesis Example 1.
It is a graph which shows the measurement result of FT-IR of a polymer.

FIG. 3 is a vinyl system (co) obtained in Synthesis Example 1.
It is a graph which shows the measurement result of the proton NMR of a polymer.

FIG. 4 is a vinyl system (co) obtained in Synthesis Example 1.
It is a graph which shows the measurement result of the dynamic viscoelasticity of a polymer.

FIG. 5 is a graph showing the measurement results of the molecular weight distribution of the curable resin composition obtained in Synthesis Example 6.

FIG. 6 is a graph showing FT-IR measurement results of the curable resin composition obtained in Synthesis Example 6.

FIG. 7 is a graph showing the results of proton NMR measurement of the curable resin composition obtained in Synthesis Example 6.

FIG. 8 is a graph showing the measurement results of dynamic viscoelasticity of the curable resin composition obtained in Synthesis Example 6.

[Procedure amendment]

[Submission date] August 6, 2001 (2001.8.6)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] [Wherein, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and R ² represents —CO—O— (CH ₂ ) _x — (where x is an integer of 1 to 6). ), — (CH ₂ ) _x — (where x is an integer of 1 to 6), or a single bond between a carbon atom and a silicon atom, and R ³ is an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group having 1 to 6 carbon atoms and at least one of the three R ³ is an alkoxy group] and / or the following general formula (2).

[Chemical 2] [Wherein, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and R ² represents —CO—O— (CH ₂ ) _x — (where x is an integer of 1 to 6). ),-(CH ₂ ) _x- (where x is an integer of 1 to 6), or a single bond between a carbon atom and a silicon atom, and R ³ is an alkyl group having 1 to 6 carbon atoms or Carbon number 1
A single bond from a silicon atom is bonded to an oxygen atom of a siloxane bond] and a repeating unit A of vinyl polymerization represented by the following general formula (3):

[Chemical 3] (In the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, an alkenyl group, an aryl group, a hydroxyl group, and a hydrogen atom, and the same as each other. Or may be different)
A solventless liquid-type curability characterized by having a repeating unit B of a siloxane bond represented by the formula (1) in the same molecule or in a different molecule and being substantially solventless and liquid at room temperature and normal pressure. Resin composition.

[Chemical 4] (However, in the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a hydroxyl group, a hydrogen atom, and a substituted or unsubstituted alkoxy group, Which may be the same or different, at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups) and an alkoxysilane monomer represented by the general formula The solventless liquid curable resin according to claim 1, which is obtained by hydrolytic condensation in the presence of a vinyl-based (co) polymer having a hydrolyzable alkoxysilyl group in the side chain represented by (1). Composition.

[Chemical 5] (However, in the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a hydroxyl group, a hydrogen atom, and a substituted or unsubstituted alkoxy group, Which may be the same or different, at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups) and an alkoxysilane monomer represented by the general formula A resin mixture obtained by hydrolysis and condensation in the presence of a part of a vinyl-based (co) polymer having a hydrolyzable alkoxysilyl group in the side chain represented by (1) and the vinyl-based (co) polymer The solventless liquid curable resin composition according to claim 1, which is obtained by mixing with the rest of the coalescence.

[Chemical 6] (However, in the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a hydroxyl group, a hydrogen atom, and a substituted or unsubstituted alkoxy group, Which may be the same or different, and at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups) are hydrolyzed and condensed to form an alkoxysilane monomer or a partially hydrolyzed condensate thereof. The solventless liquid type curable resin composition according to claim 1, which is obtained by mixing the organopolysiloxane obtained by the above-mentioned method in a predetermined ratio.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

(Wherein R ⁴ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, hydroxyl group, hydrogen atom)
And a substituent selected from the group consisting of a child and a substituted or unsubstituted alkoxy group, which may be the same or different from each other, and at least two of the four R ⁴ are substituted or unsubstituted. The alkoxysilane monomer represented by (which is an alkoxy group) or a partial hydrolysis-condensation product thereof is hydrolyzed and condensed.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

The obtained coating compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were applied on a bonderite steel plate using an applicator and then dried and cured at room temperature for 7 days to give an appearance of cured film, In addition to examining surface hardness (after 1 and 7 days), chemical resistance, long-term water resistance, high-concentration organic acid resistance, thick coatability, dynamic viscoelasticity E'retention rate, weather resistance, and baking crack resistance, MIBK A rubbing test and a boiling test were performed.
In addition, when evaluating the thick coating property, a 10 mil applicator
20mil app when evaluating dynamic viscoelasticity E'using
When using a caterer and when evaluating other physical properties
A 5 mil applicator was used. The test method of each performance test is as follows, and the results are shown in Table 3 together with the coating composition.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 143/04 C09D 143/04 183/10 183/10 F term (reference) 4J002 BG02Y CP12W CP12X GH01 4J035 BA01 CA13 CA14 LA03 LB01 4J038 CC061 CE051 CF021 CG141 CG161 CG171 CH031 CH041 CH071 CH081 CH121 CH171 CH201 CH251 CJ181 CJ291 DB221 DL021 DL031 DL111 DL121 DL151 KA04 LA02 NA01 NA03 NA04 NA05 NA11 NA12 NA14 NA27 PA18 PC08 PB05 PC02

Claims (7)

[Claims] 1. The following general formula (1): [Wherein, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and R ² represents —CO—O— (CH ₂ ) _x — (where x is an integer of 1 to 6). ), — (CH ₂ ) _x — (where x is an integer of 1 to 6), or a single bond between a carbon atom and a silicon atom, and R ³ is an alkyl group having 1 to 6 carbon atoms, Or an alkoxy group having 1 to 6 carbon atoms and at least one of three R ³ is an alkoxy group] and / or the following general formula (2) [Wherein, R ¹ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, and R ² represents —CO—O— (CH ₂ ) _x — (where x is an integer of 1 to 6). ),-(CH ₂ ) _x- (where x is an integer of 1 to 6), or a single bond between a carbon atom and a silicon atom, and R ³ is an alkyl group having 1 to 6 carbon atoms or Carbon number 1
A single bond from a silicon atom is bonded to an oxygen atom of a siloxane bond] and a repeating unit A of vinyl polymerization represented by the following general formula (3): (In the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, an alkenyl group, an aryl group, a hydroxyl group, and a hydrogen atom, and the same as each other. Or may be different)
A solventless liquid-type curability characterized by having a repeating unit B of a siloxane bond represented by the formula (1) in the same molecule or in a different molecule and being substantially solventless and liquid at room temperature and normal pressure. Resin composition. 2. The following general formula (4): (However, in the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a hydroxyl group, and a substituted or unsubstituted alkoxy group, and they are the same as each other. May be different or different, and at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups), and an alkoxysilane monomer represented by the general formula (1) The solventless liquid curable resin composition according to claim 1, which is obtained by hydrolytic condensation in the presence of a vinyl-based (co) polymer having a hydrolyzable alkoxysilyl group in the side chain represented by. 3. The following general formula (4): (However, in the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a hydroxyl group, and a substituted or unsubstituted alkoxy group, and they are the same as each other. May be different or different, and at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups), and an alkoxysilane monomer represented by the general formula (1) The resin mixture obtained by hydrolytic condensation in the presence of a part of the vinyl-based (co) polymer having a hydrolyzable alkoxysilyl group in the side chain represented by and the rest of the vinyl-based (co) polymer The solventless liquid type curable resin composition according to claim 1, which is obtained by mixing and. 4. A vinyl-based (co) polymer having a hydrolyzable alkoxysilyl group in the side chain represented by the general formula (1), using the curable resin composition according to claim 2 as a compatibilizer. The following general formula (4): (However, in the formula, R ⁴ is a substituent selected from the group consisting of a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a hydroxyl group, and a substituted or unsubstituted alkoxy group, and they are the same as each other. May be different or different, and at least two of the four R ⁴ are substituted or unsubstituted alkoxy groups) obtained by hydrolyzing and condensing an alkoxysilane monomer represented by or a partially hydrolyzed condensate thereof. The solventless liquid type curable resin composition according to claim 1, which is obtained by mixing the organopolysiloxane to be prepared in a predetermined ratio. 5. The proportion of the repeating unit A of vinyl polymerization and the repeating unit B of siloxane bond is 0.5 to 50% by weight of the repeating unit A and 50 to 9 of the repeating unit B.
The solventless liquid curable resin composition according to any one of claims 1 to 4, which is 9.5% by weight. 6. A solvent-free liquid type curable resin composition according to claim 1 and a condensation catalyst having a catalytic action for forming a siloxane bond as essential components, and is substantially solvent-free. A coating composition for forming a cured film, which is liquid at room temperature and atmospheric pressure. 7. The coating composition for forming a cured film according to claim 6, wherein the formed cured film is substantially transparent.