JP2001064350A - Polymerizable composition and structure coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable composition which excels in polymerizability and whose polymerize excels in flexibility, heat resistance, and weatherability, and a structure coating material composed the polymerizable composition. SOLUTION: This polymerizable composition comprises (A) an alkyl (meth) acrylate, (B) a polymer having a radically polymerizable group and a number average molecular weight of 1,000-30,000, (C) a wax having a melting point of not lower than 50 deg.C, and (D) a radical polymerization initiator. As the component (B), a vinyl polymer is preferred. The amounts of component (A), component (B), component (C), and component (D) based on the sum of component (A) and component (B) are 30-85 wt.%, 15-70 wt.%, 0.3-5 wt.%, and 0.01-10 wt.%, respectively. A structure coating material to be utilized as a coating material and a waterproofing agent can be obtained from the polymerizable composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkyl acrylate or an alkyl methacrylate [hereinafter referred to as an alkyl (meth) acrylate. ] And a specific polymer having a radical polymerizable group as a main component, having excellent weather resistance and long-term flexibility, and capable of being applied in a short period of time, and a coating for a structure comprising the polymerizable composition. It relates to the agent. The polymerizable composition includes a paint, a waterproofing agent,
It is useful in the technical fields such as floor coatings, sealing agents, injections and adhesives.

[0002]

2. Description of the Related Art In order to prevent deterioration of concrete and steel used in buildings and structures, the surface thereof is coated with various compositions such as epoxy resin, urethane resin and unsaturated polyester resin. However, these compositions have a problem that a long construction period is required because the time required for polymerization is long. In particular, the polymerizability decreases significantly in winter, etc.
Limited use.

[0003] In order to solve the above-mentioned problems, there has been proposed a composition containing alkyl (meth) acrylate and a polymer having no radical polymerizable group as main components (Japanese Patent Publication No. 1-36508). Gazette). This composition has a short time required for polymerization and has good polymerizability at low temperatures.

[0004]

SUMMARY OF THE INVENTION However,
The resin composition described in 36508 is mainly composed of an alkyl (meth) acrylate and a polymer having no radical polymerizable group, but is used because of insufficient tensile strength and elongation. Is restricted. When the polymer having no radical polymerizable group has a large molecular weight, the tensile strength and the elongation are improved, but at the same time, the composition becomes high in viscosity and the handling workability becomes poor. Those to which a plasticizer or the like is added to improve handling operability may have poor heat resistance and weather resistance leading to a decrease in elongation over time and the like, and thus use is also limited. .

The present invention has been made by paying attention to such problems existing in the prior art. The purpose is to excel in handling workability and polymerizability,
It is an object of the present invention to provide a polymerizable composition in which an obtained polymer has a large elongation, that is, excellent flexibility, heat resistance, and good weather resistance, and a structure coating agent comprising the polymerizable composition. is there.

[0006]

Means for Solving the Problems To achieve the above object, the polymerizable composition according to the first aspect of the present invention comprises (A)
Alkyl acrylate or alkyl methacrylate,
(B) having a radical polymerizable group and having a number average molecular weight of 1,0
The polymer is composed of a polymer having a melting point of not less than 50 ° C. and a (D) radical polymerization initiator.

[0007] The polymerizable composition of the invention according to claim 2 comprises:
The invention according to claim 1, wherein the component (B) is a vinyl polymer. The polymerizable composition according to the third aspect of the present invention is the polymerizable composition according to the first or the second aspect, based on the total amount of the components (A) and (B).
The proportions of the components (A), (B), (C) and (D) are 30 to 85% by weight, 15 to 70% by weight, respectively.
0.3 to 5% by weight and 0.01 to 10% by weight.

[0008] A coating material for a structure according to the present invention according to claim 4 comprises the polymerizable composition according to any one of claims 1 to 3.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The polymerizable composition has (A) an alkyl (meth) acrylate, (B) a polymer having a radical polymerizable group, a number average molecular weight of 1,000 to 30,000, and (C) a melting point of 50 ° C or more. It comprises waxes and (D) a radical polymerization initiator.

Therefore, the component (A) will be described first. The alkyl (meth) acrylate of the component (A) is a main component of the polymerizable composition and exhibits basic physical properties such as flexibility, heat resistance and weather resistance, and various types are used. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2 -Ethoxyethyl (meth) acrylate and isobornyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like.

Next, the component (B) will be described. The polymer having a radical polymerizable group of the component (B) and having a number average molecular weight of 1,000 to 30,000 (hereinafter, referred to as a polymer having a radical polymerizable group) includes the polymer having a radical polymerizable group and the component (A). Reactive, having a radical polymerizable group in terms of compatibility,
A vinyl polymer having a number average molecular weight of 1,000 to 30,000, and a (meth) acrylic polymer is preferred.
The (meth) acrylic polymer means a polymer having a monomer unit having a (meth) acryloyl group as a main component.

The number average molecular weight of the radical polymerizable group-containing polymer must be 1,000 to 30,000. The reason is that when the number average molecular weight is less than 1,000, the resulting polymer has low strength,
If it exceeds 00, the composition described later has high viscosity and poor workability.

Here, the number average molecular weight and the weight average molecular weight are values in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a solvent.

The radical polymerizable group in the radical polymerizable group-containing polymer includes a vinyl group, and specifically includes a (meth) acryloyl group and an allyl group. The number of radically polymerizable groups in the radically polymerizable group-containing polymer is preferably 1 to 5, more preferably 2 to 3, per molecule of the polymer. If the number of radically polymerizable groups is less than 1, the strength of the obtained polymer may be weak, and if it is 6 or more, the flexibility may be reduced.

The radical polymerizable group-containing polymer plays an important role in controlling the viscosity of the polymerizable composition, shortening the polymerization time, reducing polymerization shrinkage, and imparting strength and flexibility to the polymer. Component.

As the polymer having a radical polymerizable group, those synthesized by various means can be used. For example, a polymer having a reactive functional group such as a hydroxyl group, an isocyanate group, an amino group and an acetoacetoxy group can be used. (Hereinafter, referred to as a functional group-containing polymer), and a compound having a group capable of reacting with the functional group and a radical polymerizable group with respect to the functional group-containing polymer (hereinafter, a compound for introducing a radical polymerizable group) And the like). Radical polymerizable group-containing polymer obtained by such a reaction, the polymer obtained from the polymerizable composition described later, tensile strength, flexibility, heat resistance, in order to make more excellent physical properties such as weather resistance. It is preferred. The functional group-containing polymer is a polymer having a functional group having reactivity as described above.However, a vinyl polymer having the functional group is to have more excellent physical properties such as heat resistance and weather resistance. It is preferred. Such a functional group-containing polymer is a vinyl monomer having a reactive functional group exemplified below (hereinafter, referred to as a vinyl monomer).
It is called a functional group-containing vinyl monomer. ) Can be produced by polymerizing with other vinyl monomers as necessary.

Examples of the functional group-containing vinyl monomer include a vinyl monomer having a hydroxyl group, a vinyl monomer having an isocyanate group, a vinyl monomer having an amino group, a vinyl monomer having an acetoacetoxy group, Examples thereof include a vinyl monomer having a carboxyl group.

As the vinyl monomer having a hydroxyl group, various ones can be used. For example, hydroxyethyl (meth)
Mono- or poly (meth) of polyhydric alcohols such as hydroxyalkyl (meth) acrylates such as acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, and pentaerythritol tri (meth) acrylate and glycerin mono (meth) acrylate Acrylates and adducts of epoxides with (meth) acrylic acid, such as adducts of cyclohexene oxide with (meth) acrylic acid, are mentioned.

Examples of the vinyl monomer having an isocyanate group include 2-methacryloyloxyethyl isocyanate, dimethyl meta-isopropenylbenzyl isocyanate and the like.

Examples of the vinyl monomer having an amino group include:
Allylamine, diallylamine and the like can be mentioned. Examples of vinyl monomers having an epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl methacrylate, and allyl Glycidyl ether and the like.

Examples of the vinyl monomer having an acetoacetoxy group include acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, and 2.
3-di (acetoacetoxy) propyl methacrylate and the like.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, cinnamic acid, and an equimolar condensate of a hydroxyl group-containing (meth) acrylate and maleic acid.

Other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate and isobornyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) A) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and the like.

The functional group-containing polymer can be obtained by a known polymerization method. When the polymer is a vinyl polymer,
What is obtained by continuously polymerizing the above vinyl monomer at a high temperature of 160 to 350 ° C is preferable. According to this high-temperature continuous polymerization method, a polymer having a reactive group having a relatively low molecular weight can be obtained, and the composition described later has low viscosity and good workability. Furthermore, the polymerization method does not require the use of a polymerization initiator, or a polymer having a desired molecular weight can be obtained with a small amount of use even when a polymerization initiator is used, so that the polymer generates radical species by heat or light. It has high purity and hardly contains such impurities, and has excellent weather resistance and heat resistance.

The high temperature continuous polymerization is described in JP-T-57-50217.
No. 1, JP-A-59-6207, JP-A-60-
This can be achieved by a known method disclosed in, for example, JP-A-215007. For example, filling a pressurizable reactor with a solvent,
After setting to a predetermined temperature under pressure, the monomer mixture, and if necessary, the radical polymerization initiator and the solvent are supplied to the reactor at a constant supply rate, and a method of extracting a reaction liquid in an amount corresponding to the supply amount is used. No.

When a solvent is used, the solvent to be charged into the reactor before the start of the reaction and the solvent to be supplied may be the same or different. The solvent can be appropriately determined in consideration of the solubility of the monomer or the polymer, but preferably has no reactivity with the above functional group. Ethers such as diethylene glycol ethyl ether are preferred solvents. The proportion of the solvent used is 20 parts by weight per 100 parts by weight of the monomer mixture.
It is preferably 0 parts by weight or less.

As the radical polymerization initiator, peroxide,
Known compounds such as azo compounds can be used, but peroxides are preferred. The usage ratio of the radical polymerization initiator is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the monomer mixture.

The reaction temperature is preferably from 160 to 350 ° C.
When the temperature is lower than 160 ° C., the molecular weight of the obtained polymer may be too large or the reaction rate may be slow. On the other hand, when the temperature is higher than 350 ° C., a decomposition reaction occurs and a reaction solution is formed. Coloring may be seen. The pressure depends on the reaction temperature and the boiling point of the monomer mixture and the solvent used, and does not affect the reaction, but may be any pressure that can maintain the reaction temperature.

The residence time of the monomer is preferably from 2 to 60 minutes. When the residence time is less than 2 minutes, the yield of the functional group-containing polymer tends to be low, and when it exceeds 60 minutes, the productivity is slightly lowered.

As the compound for introducing a radical polymerizable group,
For example, a polymer having a hydroxyl group has a (meth) acrylate having an isocyanate group such as 2-methacryloyloxyethyl isocyanate, and a polymer having a carboxyl group has a (meth) acrylate having an epoxy group such as glycidyl methacrylate. For polymers having an acrylate or amino group, (meth) acrylates having an acetoacetoxy group, such as acetoacetoxyethyl (meth) acrylate, may be mentioned. The reaction between the functional group-containing polymer and the compound for introducing a radical polymerizable group may be performed according to a usual method. When reacting these, a known catalyst can also be used.

Next, when a wax having a melting point of 50 ° C. or more, which is a component (C), is polymerized as a coating film, the wax is distributed at a high concentration on the surface of the coating film. The purpose of this is to prevent the acidic components from coming into contact with oxygen in the air and to improve the polymerizability of the composition.
Waxes mean a collection of substances similar to wax in a narrow sense, such as oils and fats, paraffin wax, and the like, as well as wax in a narrow sense. Such waxes have a melting point of 50 ° C.
Examples of the above-mentioned paraffin wax, polyethylene wax, higher fatty acids such as stearic acid, and the like. Melting point 50
Those having a temperature of lower than ℃ are unsuitable because they are easily melted and cannot exert the above-mentioned effect of improving the polymerizability.

Next, the radical polymerization initiator of the component (D) is blended to polymerize the components (A) and (B). As this radical polymerization initiator, a redox initiator composed of an oxidizing agent and a reducing agent is preferable. The type of the redox initiator is not particularly limited, and a known one can be used.

The oxidizing agent constituting the redox initiator is not particularly limited, but it is preferable to use an organic peroxide. Examples of the organic peroxide include diacyl peroxide, peroxyester, hydroperoxide, dialkyl peroxide, ketone peroxide, peroxyketal, and alkylperester. These organic peroxides are appropriately selected and used depending on various conditions at the time of construction such as kneading conditions and curing temperature. Among them,
It is particularly preferable to use benzoyl peroxide surface-treated with an inorganic powder having water of crystallization.

Examples of the inorganic powder include dicalcium phosphate, calcium sulfate, magnesium carbonate, aluminum hydroxide and the like. These organic peroxides are diluted with an inert liquid or powder having a concentration of preferably 50% or less, more preferably 35% or less, and particularly preferably 30% or less, because of their excellent handleability. It is preferable to use a paste or powder.

Various reducing agents can be used, and examples thereof include tertiary amines and metal soaps containing metals such as cobalt, vanadium and manganese. These may be used in combination of two or more.

As the tertiary amine, it is preferable to use one in which at least one aromatic residue is directly bonded to a nitrogen atom. For example, N, N'-dimethylaniline, N,
N'-dimethyl-p-toluidine. Particularly preferred are the above tertiary amines having one or more hydroxyl groups, such as N, N′-di (β-hydroxyethyl) -aniline, N-methyl-N′-hydroxyethylaniline, N-ethyl, N′-β-hydroxyethyl-aniline, N, N′-di (β-hydroxyethyl) -m-toluidine, N, N′-di (β-hydroxyethyl) -p-toluidine, N-methyl, N ′ -Β-hydroxyethyl-m-toluidine, N-ethyl, -N′-β-hydroxyethyl-m-toluidine, NN ′
-Di (β-hydroxyethyl) m-chloro-aniline and the like.

The polymerizable composition of the present invention comprises the component (A)
It consists of component (B), component (C) and component (D), and is prepared by uniformly mixing these components. When component (D) is a redox initiator,
A mixture comprising the components (A), (B), (C) and the reducing agent and a component comprising the oxidizing agent are separately prepared, and the two-pack type, which mixes both immediately before use, has a good storage stability. It is preferable because it is good.

The preferred proportions of the above components are as follows. The ratio of the component (A) to the total amount of the components (A) and (B) is preferably from 30 to 85% by weight, more preferably from 50 to 75% by weight. If the proportion of the component (A) is less than 30% by weight, the composition has a high viscosity, so that the workability and leveling property may be reduced. On the other hand, if it exceeds 85% by weight, the composition is poor in polymerizability. Or the polymer may have poor adhesion to the substrate as a film due to polymerization shrinkage.

The proportion of the component (B) is preferably from 15 to 70% by weight, more preferably from 25 to 50% by weight, based on the total amount of the components (A) and (B). If the proportion of the component (B) is less than 15% by weight, the polymerizability of the composition may be reduced. If it exceeds 70% by weight, the polymerization time is shortened, but the viscosity of the composition increases and the workability and Leveling properties may decrease.

The proportion of the component (C) is preferably from 0.3 to 5% by weight, more preferably from 0.5 to 3% by weight, based on the total amount of the components (A) and (B). When the proportion of the component (C) is less than 0.3% by weight, a sufficient air blocking effect cannot be obtained, and the composition may be poor in polymerizability. May have a poor appearance.

The proportion of the component (D) is preferably 0.01 to 10% by weight based on the total amount of the components (A) and (B). When the component (D) is a redox-based polymerization initiator, each of the oxidizing agent and the reducing agent is 0.01 to 10%.
% By weight. If this proportion is less than 0.01% by weight, the composition may be poor in polymerizability. If it exceeds 10% by weight, impurities such as decomposition products of a polymerization initiator increase in the polymer, resulting in poor weather resistance. In some cases.

The polymerizable composition of the present invention may contain a radical polymerizable monomer other than the component (A), if necessary. Specific examples thereof include styrene, acrylonitrile, methacrylonitrile, and vinyl acetate. The addition amount is preferably 100 parts by weight or less based on 100 parts by weight of the component (A).
More preferably, it is 50 parts by weight or less.

The polymerizable composition may contain, if necessary, an antifoaming agent or a leveling agent of silicone type or acrylic type, an ultraviolet absorber of benzotriazole type, benzophenone type or salicylic acid type, hydroquinone, hydroquinone monomethyl ether, etc. Can be added.
The amount of these additives is 0.0001 parts by weight or more based on 100 parts by weight of the total of the components (A) and (B).
It is preferable that the amount is not more than part by weight.

Further, barium sulfate, silicon oxide, talc,
Fillers such as mica, kaolin clay and calcium carbonate, and coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black and iron oxide can be added. Further, a thixotropic agent such as silica powder such as asbestos, sepiolite and aerosil can be added.

When the component (D) is a redox-based polymerization initiator, the additives such as the filler and the pigment may be added in consideration of the storage stability of the polymerizable composition and the components (A) and (B). It is preferable to mix the component, the component (C) and the reducing agent immediately before or immediately after mixing the oxidizing agent. The amount of these additives is preferably 400 parts by weight or less based on 100 parts by weight of the total of the components (A) and (B).

The method for applying the polymerizable composition includes a method using a roller, a lake, a trowel and a spray, and the method for injecting or filling is a method using a caulking gun, a spatula, a spatula and a trowel. Is mentioned.

Next, the coating material for a structure is composed of the above polymerizable composition. This polymerizable composition is excellent in polymerizability as described above, and the obtained polymer is excellent in flexibility, heat resistance, and weather resistance.
Coating agents such as paints, waterproofing agents, wall materials and painted floor materials,
It can be used for various applications such as sealing agents, fillers, binders and adhesives. Here, the structure means a floor, a road, a building, a storage tank, or the like. Among these coating applications, it is particularly suitably used as a coating agent, a paving agent, a waterproofing agent, and the like.

The effects exerted by the above embodiments will be described together. -The polymer of the component (B) has a radical polymerizable group, and has a number average molecular weight of 1,000 to 30,000. Therefore, the polymerizable composition has low viscosity and good workability, and has good polymerizability when polymerized and polymerized by the radical polymerization initiator of the component (D). It polymerizes with the alkyl (meth) acrylate of the component (A). And the obtained polymer is excellent in flexibility, heat resistance and weather resistance.

The polymer of the component (B) is a polymer having a radical polymerizable group, preferably a polymer having a vinyl polymer having a radical polymerizable group, and more preferably a (meth) acryl having a radical polymerizable group. It is obtained by reacting a polymer containing a functional group such as a hydroxyl group, an isocyanate group, an amino group and an acetoacetoxy group with a compound having a group capable of reacting with the functional group and a radical polymerizable group. For this reason, the physical properties such as the glass transition temperature and the compatibility of the polymer obtained by the reaction of the polymer of the component (B) or the component (A) can be changed, and the molecular design of the polymer can be easily performed. it can.

Since the coating agent for structures such as buildings is composed of the polymerizable composition having the excellent physical properties as described above, it can be suitably used as a paint, a waterproofing agent, an adhesive and the like. . In that case, the coating material for a structure is excellent in polymerizability, so that short-term construction is possible.

[0051]

The above embodiment will be described more specifically with reference to production examples, examples and comparative examples. In the following, parts and% are based on weight. (Production Example 1) A 300 ml capacity pressurized stirred tank reactor equipped with an electric heater was filled with diethylene glycol monoethyl ether, the temperature was set to 145 ° C, and the pressure was adjusted to 25 to 27 kg / g by a pressure regulator. It was kept at cm ^2.

Then, while keeping the pressure of the reactor constant, 3 parts of hydroxyethyl methacrylate, 57 parts of 2-ethylhexyl acrylate, and 4 parts of methyl methacrylate
A mixture of a monomer and a polymerization initiator A-1 comprising 0 parts and 0.2 parts of di-t-butyl peroxide was fed at a constant feed rate [23 g / min. (Referred to as residence time) of 13 minutes], the continuous supply from the raw material tank to the reactor was started, and the mixture A-
The reactor contents corresponding to the feed amount of 1 were continuously withdrawn from the outlet. Immediately after the start of the supply of the mixture A-1 of the monomer and the polymerization initiator, the reaction temperature temporarily decreased, and then a temperature increase considered to be caused by polymerization heat was observed. It was kept at １８182 ° C.

After the start of the supply of the mixture A-1 of the monomer and the polymerization initiator, the reaction liquid extracted for 60 minutes from the time when the temperature in the reactor became stable was collected. During this time, 1380 g of a simple substance and a mixture A-1 of a polymerization initiator were supplied, and 1338 g of a reaction solution was recovered.

Subsequently, the reaction solution was introduced into a thin film evaporator,
Volatile components such as unreacted monomers were separated to obtain 1230 g of a concentrated liquid. The unreacted monomer in the concentrate was measured using a gas chromatograph equipped with an FID detector, but was below the lower limit of detection. Hereinafter, the above concentrate is referred to as polymer B
It is called -1. The number average molecular weight (hereinafter abbreviated as Mn) of the polymer B-1 determined by GPC was 9,200, the weight average molecular weight (hereinafter abbreviated as Mw) was 19,300, and the degree of dispersion (Mw / Mn). ) Was 2.1. Polymer B
The hydroxyl value of -1 was 12.9 mgKOH / g. (Production Example 2) A 300 ml capacity pressurized stirred tank reactor equipped with an electric heater was filled with diethylene glycol monoethyl ether, the temperature was adjusted to 145 ° C, and the pressure was adjusted to 25 to 27 kg / g by a pressure regulator. It was kept at cm ^2.

Then, while keeping the reactor pressure constant, a monomer comprising 2 parts of acrylic acid, 58 parts of n-butyl acrylate, 40 parts of methyl methacrylate and 0.2 part of di-t-butyl peroxide was polymerized. Initiator mixture A-2
Is continuously supplied from the raw material tank to the reactor at a constant supply rate (23 g / min, corresponding to a residence time of 13 minutes), and the reaction corresponding to the supply amount of the mixture A-2 of the monomer and the polymerization initiator is started. The vessel contents were continuously withdrawn from the outlet. Immediately after the start of the supply of the mixture A-2 of the monomer and the polymerization initiator, the reaction temperature temporarily decreased, and then a temperature increase considered to be caused by the heat of polymerization was observed.
It was kept at 1-182 ° C.

After the start of the supply of the mixture A-2 of the monomer and the polymerization initiator, the reaction liquid extracted for 60 minutes from the time when the temperature in the reactor became stable was collected. During this time, 1390 g of a mixture A-2 of a monomer and a polymerization initiator was supplied, and 1340 g of a reaction solution was recovered.

Subsequently, the reaction solution was introduced into a thin film evaporator,
Volatile components such as unreacted monomers were separated to obtain 1233 g of a concentrated solution. According to gas chromatography, no unreacted monomer was present in the concentrated liquid. Hereinafter, the concentrated solution is referred to as polymer B-2. Mn of polymer B-2 determined by GPC was 14,000, Mw was 30,800, and dispersity was 2.2. The acid value of the polymer B-2 is
It was 21.3 mgKOH / g. (Production Example 3) 3 parts of hydroxyethyl methacrylate, 2
-A monomer mixture A-3 consisting of 57 parts of ethylhexyl acrylate and 40 parts of methyl methacrylate was prepared.

In a four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel, a nitrogen blowing tube and a stirrer, 15 parts of the monomer mixture A-3 and methyl isobutyl ketone (hereinafter referred to as MIBK) were added. 100 parts and 1,2,2′-azobisisobutyronitrile were charged, and the polymerization reaction was started at 80 ° C. while blowing nitrogen. After this, 2,2'-
A polymerization reaction was carried out by continuously dropping 30 parts of a solution of 5 parts of azobisisobutyronitrile in 25 parts of MIBK and 85 parts of the monomer mixture A-3 over 6 hours.

Subsequently, the solvent was distilled off from the obtained reaction solution under reduced pressure.
By leaving, polymer B-3 was obtained. Determined in the same manner as in Production Example 1.
Mn of the polymer B-3 was 9,000 and Mw was 25,10.
0, the degree of dispersion is 2.8, and the hydroxyl value is 12.6 mgKOH /
g. (Example 1) 29 parts of the polymer B-1 obtained in Production Example 1
At room temperature, 50 parts of methyl methacrylate,
Dissolved in 20 parts of xyl methacrylate. 2-methacrylo
1 part yloxyethyl isocyanate, dibutyltin di
Add 0.001 part of laurate and stir at 60 ° C for 8 hours.
The polymer C-1 and methyl methacrylate were reacted with stirring.
To obtain a mixture of methacrylate and 2-ethylhexyl methacrylate.
Was. The reaction solution collected over time is analyzed by an infrared spectrophotometer.
2240 cm due to isocyanate groups ^-1Absorption of
The completion of the reaction was confirmed by disappearance of the peak. Obtained weight
Merged C-1 is 2-methacryloyloxyethyl isocyanate
Having a methacryloyl group derived from an anate
You.

Mixture 10 of the obtained polymer C-1 and methyl methacrylate and 2-ethylhexyl methacrylate
0 parts, 2 parts of N-ethyl-N′-hydroxyethyl-m-toluidine, 1 part of paraffin wax having a melting point of 60 to 62 ° C., cobalt naphthenate [cobalt content 6%, manufactured by Dainippon Ink Co., Ltd.] 0.2 Was added to obtain Composition D-1.

For 100 parts of the composition D-1, 5 parts of titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.) and 50 parts of the active ingredient
% Of benzoyl peroxide was added and mixed well to prepare a polymerizable composition. The polymerizable composition was poured into a frame made of a Teflon plate and polymerized at room temperature to obtain a polymer having a thickness of about 1 mm.

The polymer for the compression test was 40 mm × 40 mm × 160 m
m using a metal formwork. The following evaluation was performed about the said polymerizable composition and the obtained polymer. Table 1 shows the results. (Polymerizability) With respect to the polymerizable composition immediately after the addition of the polymerization initiator, the polymerization time required until the tack disappeared at room temperature was measured. (Tensile properties) The tensile strength and elongation of the polymer were measured at a tensile speed of 200 mm / min according to JIS K 6301. (Heat resistance) The polymer was measured for tensile strength and elongation after being allowed to stand at 110 ° C. for 7 days, and expressed as a percentage (hereinafter referred to as “retention”) when compared with the initial value. Also,
The appearance change after heating was observed and indicated by the following evaluation.

…: Almost no change, Δ: slight yellowing, ×: considerable yellowing The (weather-resistant) polymer was subjected to black panel temperature 63 using a carbon arc type sunshine weather meter.
The tensile strength and elongation after irradiation at 500C for 500 hours were measured and expressed as a percentage (hereinafter referred to as "retention") when compared with the initial value. Further, changes in appearance after the test were observed and indicated by the following evaluation.

…: Almost no change, Δ: slight yellowing, ×: considerable yellowing (Compressive strength) The polymer was measured according to JIS K6911, and the compressive strength was calculated by the following equation. Compressive strength = Maximum compressive load / Compressed area (Example 2) To 28 parts of the polymer B-2 obtained in Production Example 2, 20 parts of 2-ethylhexyl acrylate, 0.54 part of tetrabutylammonium bromide, and 0.4 part of hydroquinone were added. Then, nitrogen gas containing 5% oxygen was supplied into the system at a flow rate of 20 ml / min.
Heated to 5 ° C. Glycidyl methacrylate (1.45 parts) was slowly added dropwise, and after completion of the addition, the mixture was heated to 90 ° C and reacted for 8 hours to obtain a mixture of polymer C-2 and 2-ethylhexyl acrylate.

The reaction was followed by gas chromatography, and the completion of the reaction was confirmed by disappearance of the peak due to glycidyl methacrylate. Polymer C-2
Has a methacryloyl group derived from glycidyl methacrylate.

To 50 parts of the mixture of the obtained polymer C-2 and 2-ethylhexyl acrylate, 50 parts of methyl methacrylate, N-ethyl-N'-hydroxyethyl-m-
Composition D-2 was added with 2 parts of toluidine, 1 part of paraffin wax having a melting point of 60 to 62 ° C, and 0.2 part of cobalt naphthenate (cobalt content: 6%: manufactured by Dainippon Ink Co., Ltd.).
I got Using the obtained composition, a polymerizable composition was prepared in the same manner as in Example 1, and a polymer was produced and evaluated. Table 1 shows the results. (Example 3) 29 parts of the polymer B-3 obtained in Production Example 3 was dissolved in 50 parts of methyl methacrylate and 20 parts of 2-ethylhexyl methacrylate at room temperature, and 1 part of 2-methacryloyloxyethyl isocyanate and dibutyltin were dissolved. 0.001 part of dilaurate was added and reacted by stirring at 60 ° C. for 8 hours. Polymer C-3 and methyl methacrylate,
A mixture of 2-ethylhexyl methacrylate was obtained. The reaction solution collected over time was analyzed by an infrared spectrophotometer, and the completion of the reaction was confirmed by disappearance of the absorption peak at 2240 cm ^-1 due to the isocyanate group. The obtained polymer C-3 has a methacryloyl group derived from 2-methacryloyloxyethyl isocyanate.

Mixture 10 of the obtained polymer C-3 and methyl methacrylate and 2-ethylhexyl methacrylate
In 0 parts, 2 parts of N-ethyl-N′-hydroxyethyl-m-toluidine, 1 part of paraffin wax having a melting point of 60 to 62 ° C., cobalt naphthenate (cobalt content: 6%, manufactured by Dainippon Ink Co., Ltd.) 0.2 Parts of the composition D-
3 was obtained. Using the obtained composition, a polymerizable composition was prepared in the same manner as in Example 1, and a polymer was produced and evaluated. Table 1 shows the results. (Comparative Example 1) 30 parts of the polymer B-1 obtained in Production Example 1 was dissolved at room temperature in 50 parts of methyl methacrylate and 20 parts of 2-ethylhexyl methacrylate, and N-ethyl-
N'-hydroxyethyl-m-toluidine 2 parts, melting point 6
1 part of paraffin wax at 0 to 62 ° C, cobalt naphthenate (cobalt content 6%, manufactured by Dainippon Ink and Chemicals, Inc.)
0.2 part was added and mixed to obtain a composition D-4. Using the obtained composition, a polymerizable composition was prepared in the same manner as in Example 1, and a polymer was produced and evaluated. Table 1 shows the results. (Comparative Example 2) Methyl methacrylate-butyl methacrylate polymer (weight ratio 70/30, number average molecular weight 30,0
00, weight average molecular weight 72,000) 30 parts of methyl methacrylate 50 parts, 2-ethylhexyl acrylate 2
0 parts, 10 parts of dioctyl phthalate, 10 parts of chlorinated paraffin (chlorine content 40%), 2 parts of N, N-dimethylaniline, 1 part of paraffin wax having a melting point of 60 to 62 ° C, cobalt naphthenate (cobalt content Composition D
-5 was obtained. Using the obtained composition, a polymerizable composition was prepared in the same manner as in Example 1, and a polymer was produced and evaluated. Table 1 shows the results.

[0068]

[Table 1] As shown in Table 1, in Examples 1 to 3, polymerization time, elongation, heat resistance, and weather resistance were all good, and the overall performance was excellent. On the other hand, in Comparative Examples 1 and 2, at least one of the above performances was poor, and the overall performance was poor.

The technical idea grasped from the embodiment will be described below. The polymerizable composition according to any one of claims 1 to 3, wherein the polymer (B) is obtained by a continuous polymerization method at a polymerization temperature of 160 to 350 ° C.

In the case of such a constitution, a polymer having a low molecular weight and a high purity containing almost no impurities can be obtained, and a polymer having a low dispersity can be obtained. The polymer according to any one of claims 1 to 3, wherein the polymer (B) is formed from a polymer having a functional group, a group capable of reacting with the functional group, and a compound having radical polymerizability. Or a polymerizable composition according to any one of the above.

With such a constitution, the desired physical properties of the polymer obtained from the polymerizable composition can be improved.

[0072]

As described above, according to the present invention, the following effects are exhibited. According to the polymerizable composition of the invention according to claim 1, the polymerizable composition is excellent, and
The resulting polymer is excellent in flexibility, heat resistance and weather resistance.

According to the polymerizable composition of the invention described in claim 2, in addition to the effects of the invention described in claim 1, the polymerizability can be improved, and the physical properties of the obtained polymer can be improved.
According to the polymerizable composition of the invention described in claim 3, the effects of the invention described in claim 1 or 2 can be surely exhibited in a well-balanced manner.

According to the coating material for a structure of the invention according to the fourth aspect, the effects of the invention according to any one of the first to third aspects can be effectively exhibited, and a paint, a waterproofing agent, It can be suitably used as a floor material, a sealing agent, a filler, a binder, an adhesive and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Michihiro Kawai 1 at Funami-cho, Minato-ku, Nagoya-shi, Aichi 1 East Nagoya Co., Ltd. Nagoya Research Institute Co., Ltd. (72) Inventor Tsuguo Kimura Funami, Minato-ku, Nagoya-shi, Aichi No. 1 in the town Toagosei Co., Ltd. Nagoya Research Laboratory F term (reference) 4J034 BA03 DA01 DA05 DA08 DK00 DK06 DK08 DP18 HA02 MA22 RA07 RA08 4J038 BA212 FA121 FA122 FA231 FA232 KA03 MA14 NA03 NA14 NA23 PB05 PC02 PC04

Claims (4)

[Claims] (A) an alkyl acrylate or alkyl methacrylate, (B) a polymer having a radical polymerizable group and a number average molecular weight of 1,000 to 30,000,
A polymerizable composition comprising (C) a wax having a melting point of 50 ° C. or higher and (D) a radical polymerization initiator. 2. The polymerizable composition according to claim 1, wherein the component (B) is a vinyl polymer. 3. The ratio of the component (A), the component (B), the component (C) and the component (D) to the total amount of the component (A) and the component (B) is 30 to 85% by weight, 15 ~
The polymerizable composition according to claim 1 or 2, wherein the amount is 70% by weight, 0.3 to 5% by weight, and 0.01 to 10% by weight. 4. A structural coating comprising the polymerizable composition according to claim 1.