JPH11228645A - Acrylic syrup composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an acrylic syrup composition that can form a cured product of high strength and good weather resistance without occurrence of yellowing with time. SOLUTION: This acrylic syrup composition comprises (A) at least one of (meth)acrylate ester selected from acrylic esters and methacrylic esters, (B) a metacrylic ester macromonomer that is soluble in the component (A), (C) a plasticizer soluble in the component (A), (D) a compound of having at least two polymerizable bonds in one molecule and (E) a polymerization initiator containing a peroxide and a tertiary amine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an acrylic syrup composition.

[0002]

2. Description of the Related Art Epoxy resins, acrylic resins and the like are known as resins used for coating and coating road surfaces or floor surfaces such as concrete and asphalt. However, epoxy resin is difficult to apply thickly by one coating,
Further, the durability is poor. Further, there are disadvantages such as a slow curing speed and a long application time.

[0003] On the other hand, the acrylic syrup resin described in Japanese Patent Publication No. 1-36508 can be applied in one thick coating, has a short curing time, is excellent in durability, but has an excellent durability. The cured product tends to be colored yellow, and the weather resistance tends to be insufficient. As a polymerization initiator for polymerizing an acrylic syrup, diacyl peroxide (benzoyl peroxide) and a tertiary amine containing at least one aromatic group directly bonded to a nitrogen atom (e.g., dimethyl p- Toluidine).

In general, it is conceivable to reduce the amount of the polymerization initiator, that is, the amount of the aromatic tertiary amine, in order to suppress the yellow discoloration of the cured product and improve the weather resistance. Then, the polymerization rate of the acrylic syrup is reduced, the amount of unpolymerized monomer is increased, and the physical properties are reduced. It is also conceivable to increase the amount of the compounded polymer and decrease the compounded amount of the monomer component. However, if the compounded amount of the polymer is increased, the viscosity of the system is significantly increased, and the workability is impaired.
Further, in order to lower the viscosity of the system, it is necessary to lower the molecular weight of the compounded polymer. However, when the molecular weight is low, there is a problem that the strength of the cured acrylic syrup is remarkably reduced.

[0005]

SUMMARY OF THE INVENTION The present invention solves the problems of the prior art and provides an acrylic resin-based road marking or floor coating composition with reduced yellow discoloration which can be used to obtain a composition. An object of the present invention is to provide a system syrup composition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, the use of a specific acrylic syrup composition has enabled the above object to be achieved. And found the present invention.

That is, the present invention relates to (A) at least one selected from an acrylate ester and a methacrylate ester, (B) a methacrylate ester-based macromonomer soluble and copolymerizable in the component (A), A) a plasticizer soluble in component (A), (D) a compound having at least two polymerizable bonds in one molecule, and (E) a polymerization initiator comprising a peroxide and a tertiary amine. Acrylic syrup composition comprising:

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the composition of the present invention, the acrylate and methacrylate used as component (A) include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate and t-acrylate. -Butyl, acrylates such as 2-ethylhexylphenol EO-modified acrylate, methyl methacrylate (hereinafter may be abbreviated as MMA), ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, T-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylic acid dimethylaminoethyl, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid esters such as methacrylic acid-allylphenol EO-modified methacrylate. Among them, a glass transition temperature (hereinafter, referred to as Tg) of a homopolymer is 80 ° C. or more, for example, a mixture of methyl methacrylate and a homopolymer having a Tg of 0 ° C. or less, for example, 2-ethylhexyl acrylate Is preferably used.

[0009] In the acrylic syrup composition of the present invention, the content ratio of component (A) is from component (A) to component (C).
Is preferably in the range of 30 to 80 parts by weight based on 100 parts by weight of the total amount. When the content ratio of the component (A) is 30% by weight or more, the coating workability of the composition tends to be good, and when the content ratio is 80% by weight or less, the polymerization curability tends to be good. It is because there is.

Next, in the composition of the present invention, the component (B)
It is necessary that the methacrylic acid ester-based macromonomer used as (1) be soluble or dispersed in the component (A). Further, those having a (meth) acryloyl group or a styryl group at one terminal which can be copolymerized with the component (A) are preferably used.

As a means for producing the methacrylic acid ester-based macromonomer of the component (B), for example, a method in which 1, MMA or the like is anionically polymerized and then reacted with a halogen-containing (meth) acryloyl compound. 2. A method in which MMA or the like is radically polymerized in the presence of mercaptoacetic acid and then reacted with a glycidyl group-containing (meth) acrylic acid ester. 3. MMA or the like can be easily obtained by a group transfer polymerization method using trimethylsiloxyethyltrimethylsilyldimethylketene acetal as an initiator, followed by reaction with (meth) acryloyl chloride.

Examples of the monomers used for such methacrylic acid ester-based macromonomers include methyl methacrylate, ethyl methacrylate, and n-methacrylic acid.
-Butyl, i-butyl methacrylate, t-methacrylate
Butyl, lauryl methacrylate, 2-ethylhexyl methacrylate and the like. Preferably, a polymer of methyl methacrylate and a monomer having a low Tg of methyl methacrylate and the polymer, such as a copolymer of n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and the like Is mentioned.

[0013] The molecular weight of the methacrylic acid ester-based macromonomer used as the component (B) in the composition of the present invention is 3,000 to 100,000, preferably 5,000 to 70,000, more preferably 1,000 in terms of number average molecular weight.
It is in the range of 0 to 50,000.

In the acrylic syrup composition of the present invention, the content ratio of the component (B) is from component (A) to component (C).
Is preferably in the range of 1 to 60 parts by weight with respect to 100 parts by weight of the total amount of This means that the content ratio of component (B) is 1
When the content is not less than 60% by weight, the curing time of the composition tends to be shortened, and when the content is not more than 60% by weight, the workability of coating the composition tends to be improved. Preferably it is in the range of 15 to 50 parts by weight. By using the component (B), the component (A) can be reduced while maintaining good physical properties, and
Since the addition amount of the polymerization initiator can also be reduced, it is possible to reduce the yellow coloring of the cured product.

In the composition of the present invention, the plasticizer soluble in component (A) used as component (C) includes, for example, dibutyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, octyl Phthalates such as decyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, di-2-ethylhexyl adipate, octyl didecyl adipate, di-2-ethylhexyl sebacate, dibutyl sebacate, di-2 -Ethylhexyl sebacate, polypropylene glycol, chlorinated paraffin, adipic acid type, azelaic acid type, sebacic acid type and phthalic acid type polyester plasticizers, epoxidized oils, epoxy polymer plasticizers such as epoxidized fatty acid esters, etc. Is mentioned. These are used alone or in combination of two or more.

These plasticizers are added for the purpose of adjusting the viscosity of the acrylic syrup composition of the present invention or improving the followability to the road surface by plasticizing the cured product. It is preferable that the use ratio is in the range of 0.1 to 25 parts by weight when the total amount of the components (A) to (C) is 100 parts by weight. When the content ratio of the component (C) is 25 parts by weight or more, the cured product tends to have good stain resistance. More preferably, it is in the range of 5 to 20 parts by weight.

In the acrylic syrup composition of the present invention, the component (D) is a compound having at least two polymerizable bonds in one molecule, and is added for the purpose of improving the durability of the cured product upon curing. Component. The amount is preferably in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the total of components (A) to (C). By setting the content of the component (D) to 50 parts by weight or less,
The flexibility of the cured product tends to be good.

Specific examples of the component (D) include, for example, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-
Butylene glycol di (meth) acrylate, 1,6-
Alkanediol di (meth) acrylate such as hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Examples include acrylate, polyoxyalkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate, and divinylbenzene. These may be used alone or in combination of two or more.

The polymerization initiator used as the component (E) in the composition of the present invention comprises a peroxide and a tertiary amine. Benzoyl peroxide is preferably used as the peroxide. Benzoyl peroxide is an inert liquid or solid to avoid handling hazards and has a concentration of 5%.
It is preferable to use a paste or powder which is diluted to about 0%. In the acrylic syrup composition of the present invention, the ratio of the peroxide is 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (D). It is in the range of parts by weight.

As the tertiary amine, an aromatic tertiary amine is preferable. In particular, N, N'-dimethylaniline, N, N'-
One or a combination of two or more of dimethyl-p-toluidine, N, N'-di (hydroxyethyl) -p-toluidine, and N, N'-di (hydroxypropyl) -p-toluidine is preferred. The proportion of the tertiary amine in the acrylic syrup composition of the present invention is 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight based on 100 parts by weight of the total amount of the components (A) to (D). It is in the range of parts by weight.

The acrylic syrup composition of the present invention can be cured in a temperature range of -30.degree. C. to 50.degree. C. within 2 hours by a combination of the compounds.

The acrylic syrup composition of the present invention has a paraffin having a melting point of 40 ° C. or more for the purpose of air blocking during the curing reaction on the coating film surface, imparting gloss to the cured surface, and improving stain resistance. At least one of the waxes
Seeds can be added. Examples of the paraffin or wax include higher fatty acids such as paraffin wax, polyethylene wax, stearic acid, and 1,2-hydroxystearic acid. This paraffin or wax has a total amount of component (A) to component (D) of 100.
It is preferably used in the range of 0.1 to 5 parts by weight based on parts by weight.

In the acrylic syrup composition of the present invention, γ-methacryloxypropyltrimethoxysilane and γ-glycol are used for the purpose of stabilizing the adhesiveness to the substrate and improving the durability of the adhesive strength with the filler. A silane coupling agent such as sildoxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane can be added.

Further, in order to stabilize the curability of the composition of the present invention, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, tris (nonylphenyl) phosphite, Phosphites such as triphenyl phosphite, various antifoaming agents and leveling agents for the purpose of adjusting the surface appearance of the coating film, hydroquinone, hydroquinone monomethyl ether for the purpose of improving the storage stability of the composition of the present invention, 2,4-dimethyl-t-
A polymerization inhibitor such as butylphenol can be added.

The composition of the present invention is generally applied as a mixture mixed with aggregate and other fillers. The aggregate has an average particle diameter of 10 μm or more and an oil absorption of 25 c.
c Linseed oil / 100 g or less is preferred. Examples of these aggregates include sand, silica sand, quartz sand, colored or fired materials thereof, rock powders such as quartz powder, silica sand powder, colored porcelain, and baked, hardened and pulverized ceramic bodies, and zinc. White, calcium carbonate, alumina, glass beads and the like. In use, a combination of aggregates having different particle sizes is preferable for improving coating workability and self-leveling property.

Further, as a filler for imparting thixotropic properties to the composition, silica powder such as Aerosil can be added. As the filler, in addition to the above, it is preferable to use a coloring pigment or a dye, for example, titanium oxide,
Barium sulfate, carbon black, chromium vermillion, red iron, ultramarine, cobalt blue, phthalocyanine blue, phthalocyanine green, and the like are used. These are generally applied as a filler in an amount of from 0 to 900 parts by weight with respect to 100 parts by weight of the composition of the present invention.

The composition obtained by mixing the composition of the present invention with additives, fillers such as aggregates, etc. is used for covering floors or walls of concrete, asphalt, steel plate, etc. It is preferable to apply a primer mixture to a base such as a floor surface or a wall surface and then apply the mixture thereon.

As a construction method, a method such as a spray method, a gold iron finish, a brush coating, a roller coating and the like can be used. An application method in which the aggregate is not mixed or only a part of the mixture is applied in advance, and the aggregate is protruded to the coating film surface by spraying the aggregate before curing to impart non-slip properties It is possible.

In the composition in which the aggregate is mixed in advance, the type and amount of the aggregate are selected according to the purpose of coating.
According to the application method such as spraying, brushing, and roller coating, a relatively thin coating film, that is, 0.2 to 1 m
m can be applied, but in the case of blending for such a purpose, the amount of aggregate is determined by the composition 10 of the present invention.
It is preferable that the content is in the range of 30 to 100 parts by weight based on 0 parts by weight. When a thicker coating film, that is, a coating film of 1 to 30 mm is applied, gold iron finishing is preferable, and the amount of aggregate is preferably in the range of 100 to 900 parts by weight based on 100 parts by weight of the composition of the present invention. . In this case, it is preferable to reduce the amount of aggregate to about 100 parts by weight in order to obtain a smooth coating film surface, and to increase the amount of aggregate to 900 from an economical point of view in order to increase the thickness of the coating film. It is preferable to increase the amount to about parts by weight. However, the amount of aggregate exceeding 900 parts by weight is not preferable because the curability of the composition is deteriorated.

Further, the composition of the present invention can be used as a two-pack type (base agent and curing agent) according to the application method.

[0031]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the description, “parts” indicates parts by weight.

The evaluation methods in Examples and Comparative Examples are as follows. [Molecular weight] It was measured using gel permeation chromatography. [Yellowness (YI)] The obtained cured product was 2.5 mm thick, 1
After cutting to 0 × 20 mm, measurement was performed with a spectrum analyzer. [Bending strength] Tensilon / DTM-1-2500 (TO
YO BALDWIN).

Reference Example (Production of MMA macromonomer having methacryloyl group at one end) In 400 ml of anhydrous tetrahydrofuran (THF) under dry argon, 5.6 g (20 mmol) of trimethylsiloxyethyltrimethylsilyldimethylketene acetal was added.
and l), tris (dimethylamino) sulfate trimethylsilyl bi fluoride ^{_{(TAS + (CH 3) 3}} SiF 2 -)
0.06 g (0.23 mmol) was added and dried MM was added.
A 200 g (2.0 mol) of A was added dropwise and polymerized at 0 ° C. for 3 hours. Next, the obtained polymer was added to 6 liters of a solution containing hydrochloric acid, and the precipitate was washed with methanol, and heated at 150 ° C.
For 12 hours under vacuum. As a result, the number average molecular weight (M
n) = 11000, weight average molecular weight (Mw) = 1210
0, Mw / Mn = 1.10, 180 g of polymethyl methacrylate (polyMMA) having a hydroxyl group at one end was obtained (yield 90%).

90 g of the obtained polyMMA (having a hydroxyl content of 8.
5 mmol) was dissolved in 450 ml of anhydrous THF, 2.02 g (20.0 mmol) of tritylamine and 2.1 g (20.0 mmol) of methacryloyl chloride were added, and the mixture was reacted at room temperature for 24 hours. The reaction was added to 10 liters of methanol, and the precipitate was washed with methanol.
Vacuum dried for 2 hours. As a result, 80 g of an MMA macromonomer having a methacryloyl group at one terminal was obtained (yield 90%). The rate of introduction of the methacryloyl group into the terminal was 93% as measured by NMR. Also,
Tg measured by differential scanning calorimetry (DSC) is 102
° C.

Example 1 Methyl methacrylate 40 parts 2-Ethylhexyl acrylate 5 parts Octyldecyl phthalate 10 parts Polypropylene glycol dimethacrylate 5 parts Paraffin wax (melting point: 45 to 65 ° C.) 1 part A mixture consisting of 1 part was heated to 50 ° C. While heating and stirring, 40 parts of the MMA macromonomer having a methacryloyl group at one end obtained in Reference Example was added little by little, dissolved, and then cooled to room temperature. Thereafter, dimethyl p-toluidine 0.4
Two parts were added and mixed with stirring. Subsequently, 0.7 parts of benzoyl peroxide was added, and immediately after stirring, the mixture was applied to a thickness of about 3 mm on a polyethylene terephthalate (PET) film.
Cured in about 30 minutes. The cured product was almost transparent. A yellow index (hereinafter, referred to as an index of the yellowness of the cured product)
It is called YI value. ) Was 4.1.

Example 2 An acrylic syrup composition was cured under the same conditions as in Example 1 except that MMA = 35,000 was used as the MMA macromonomer.

Comparative Example 1 Methyl methacrylate 55 parts 2-ethylhexyl acrylate 5 parts Octyldecyl phthalate 10 parts Polypropylene glycol dimethacrylate 5 parts Paraffin wax (melting point: 45 to 65 ° C.) 1 part A mixture consisting of 1 part was heated to 50 ° C. Heat and stir with Mw =
25 parts of 40000 polyMMA was added little by little and dissolved. After cooling to room temperature, 0.6 parts of dimethyl p-toluidine was added and mixed with stirring. Subsequently, 1 part of benzoyl peroxide was added, and the mixture was quickly applied to a PET film so as to have a thickness of about 3 mm after stirring. After adding benzoyl peroxide at 20 ° C., the composition was cured in about 30 minutes. YI of cured product
The value was 20.2.

Comparative Example 2 A mixture consisting of 40 parts of methyl methacrylate, 5 parts of 2-ethylhexyl acrylate, 5 parts of octyldecyl phthalate, 5 parts of polypropylene glycol dimethacrylate, 5 parts of paraffin wax (melting point: 45 to 65 ° C.) was heated to 50 ° C. Heat and stir with Mw =
40 parts of 12000 polyMMA was added little by little and dissolved. After cooling to room temperature, 0.42 parts of dimethyl p-toluidine was added and mixed with stirring. Subsequently, 0.7 parts of benzoyl peroxide was added, and the mixture was quickly applied to a PET film so as to have a thickness of about 3 mm after stirring. After adding benzoyl peroxide at 20 ° C., the composition was cured in about 30 minutes. The YI value of the cured product was 8.3.

[Comparative Example 3] Mw = 73 instead of poly MMA
The acrylic syrup composition was cured under the same conditions as in Comparative Example 1 except that 000 MMA / n-butyl methacrylate copolymer was used.

The compositions of the syrups of each of the examples and the comparative examples and the evaluation results after the construction are collectively shown in Table 1.

[0041]

[Table 1]

The abbreviation names in Table 1 are as follows. MMA: methyl methacrylate polyfunctional monomer: polypropylene glycol dimethacrylate plasticizer: octyl decyl phthalate acrylate monomer: 2-ethylhexyl acrylate (Mw = 3500 0) Polymer 3: Polymethyl methacrylate (Mw = 40000) Polymer 4: Polymethyl methacrylate (Mw = 12000) Polymer 5: Copolymer of MMA and n-butyl methacrylate (60/40, Mw = 73000) ) BPO: benzoyl peroxide DMPT: dimethyl p-toluidine

[0043]

The acrylic syrup composition of the present invention comprises:
By blending the methacrylic acid ester-based macromonomer, it can be used as a road marking agent or a floor coating agent to provide a cured product having excellent strength and yellowing resistance.

Claims (2)

[Claims] (A) at least one selected from an acrylate ester and a methacrylate ester, (B) a methacrylate macromonomer soluble and copolymerizable in the component (A), and (C) a component (C) A plasticizer soluble in A), (D) a compound having at least two polymerizable bonds in one molecule, and (E) a polymerization initiator comprising a peroxide and a tertiary amine. Acrylic syrup composition. 2. The method according to claim 1, wherein at least one selected from acrylates and methacrylates of component (A) is 3
0 to 85 parts by weight, (B) 1 to 60 parts by weight, component (C) 0.1 to 25 parts by weight, component (D) the total amount of components (A) to component (C) 100
The composition according to claim 1, wherein the amount is 0.1 to 50 parts by weight based on parts by weight.