JPH0578545A - Acrylic syrup composition - Google Patents

Abstract

PURPOSE:To prepare the subject compsn. curable at room temp. even in summer by compounding an alkyl (meth)acrylate, a specific alkoxy (poly)alkylene glycol (meth)acrylate, an alkyl (meth)acrylate polymer, a polymerizable monomer, etc. CONSTITUTION:The objective compsn. is prepd. by compounding an alkyl (meth) acrylate, an alkoxy (poly)alkylene glycol (meth)acrylate and/or an alkylphenoxy (poly)alkylene glycol (meth)acrylate of the formula (wherein R1 is H or CH3; R2 is alkylene; R3 is alkyl or alkylphenyl; and(n) is an integer of 1-40), an alkyl (meth)acrylate (co)polymer sol. in the foregoing (meth)acrylates, a monomer having at least two polymerizable double bonds in the molecule, a paraffin wax having an m.p. of 68-80 deg.C, and a polymn. inhibitor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to floor coating materials, wall coating materials, road paving materials, in the fields of construction and civil engineering (including roads).
The present invention relates to an acrylic syrup composition used as a binder for resin mortar (concrete) and the like.

[0002]

2. Description of the Related Art Epoxy-based, urethane-based, polyester-based and acrylic-based binders have been conventionally known as binders for road paving materials, wall coating materials and the like. Of these, acrylics are attracting attention because of their fast curing speed, good chemical resistance, flexibility, and excellent load-bearing capacity for large trucks, etc. Materials, kitchen floor materials, railway station floor materials,
Widely used as asphalt concrete surface, pavement material for concrete surface, road display material, etc. (JP-A-58-196268, etc.).

[0003]

However, although the conventional acrylic syrup can be normally cured in the air whose base surface temperature is about -20 to 30 ° C., the base surface temperature is 3%.
It was difficult to cure outdoors in the summer when the temperature reached 5 to 60 ° C. That is, there are problems that the surface of the cured product is sticky even if it is cured, the cured product is softer than the ordinary cured product, and the original strength is not obtained.

For this reason, the conventional products have to be installed at night without direct sunlight, which inevitably raises labor costs and prolongs the construction period, and normally cures outdoors during the daytime in summer. There has been a strong demand for a room temperature curable acrylic syrup. The object of the present invention is to provide a base temperature of 35 to 60 ° C.
An object is to provide an acrylic syrup that normally cures even in the outdoor air in the summer.

[0005]

The gist of the present invention is (meta)
Acrylic acid alkyl ester (A), alkoxy (poly) alkylene glycol (meth) acrylic acid ester and / or alkylphenoxy (poly) alkylene glycol (meth) acrylic acid ester (B) represented by the following general formula, and the above ( (A) and (B) soluble (meth) acrylic acid alkyl ester (co) polymer (C), monomer (D) having two or more polymerizable double bonds in the molecule, melting point 68 A syrup composition comprising a paraffin wax (E) and a polymerization inhibitor (F) at -80 ° C.

[0006]

[Chemical 2]

(Wherein R ₁ is H or CH ₃ , R ₂ is an alkylene group, R ₃ is an alkyl group or an alkylphenyl group,
n is an integer of 1-40. ) Specific examples of the (meth) acrylic acid alkyl ester as the component (A) constituting the acrylic syrup composition of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. Propyl acid, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, (meth) acrylic acid t
-Butyl, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, alkyl (meth) acrylates such as lauryl (meth) acrylate, 2-hydroxy (meth) acrylate Examples thereof include hydroxyalkyl esters of (meth) acrylic acid such as ethyl, 2-hydroxypropyl (meth) acrylic acid, and 2-hydroxybutyl (meth) acrylic acid. These components (A) may be used alone or in combination of two or more kinds, but the glass transition temperature (T) such as 2-ethylhexyl acrylate (Tg = -70 ° C).
A component having a low g) deteriorates in curability when used alone, and therefore it is preferably used in combination with a component having a high Tg such as methyl methacrylate.

The component (B) is used to give flexibility to the cured product without impairing the curing characteristics of the syrup, and specifically, methoxytetraethylene glycol methacrylate and ethoxytriethylene glycol methacrylate. , Nonylphenoxytriethylene glycol acrylate, ethoxydiethylene glycol acrylate, n-butoxyethyl methacrylate, 2-phenoxyethyl methacrylate, phenoxytetraethylene glycol acrylate, nonylphenoxytetraethylene glycol acrylate, nonyl 2-ethylethoxydiethylene glycol acrylate, butoxydiethylene glycol acrylate, etc. It is illustrated. The component (B) may be used alone or in combination of two or more kinds.

The contents of the components (A) and (B) in the syrup composition are not particularly limited, but considering the viscosity of the syrup and the like, the components (A), (B), (C) and (D).
It is preferable that the total amount of (A) and (B) occupy 100 parts by weight of 60 to 90 parts by weight. Further, the content of the component (B) is preferably 30 parts by weight or less, and may be 0 parts by weight in some cases.

Component (C) is a viscosity control of the syrup composition,
It is added for the purpose of improving curability and controlling elongation and strength of the cured product. The molecular weight and the content thereof are not particularly limited, but in order to achieve the above object, the weight average molecular weight is preferably about 1,000 to 150,000, and the total of the components (A) to (D). The content of 100 parts by weight is preferably about 10 to 40 parts by weight. In addition, in order to make the viscosity of the syrup moderate, it is preferable that the content is small when the molecular weight is large and large when the molecular weight is small.

Monomers for obtaining the polymer or copolymer of the component (C) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate and methacrylic acid. Two
-Ethylhexyl, lauryl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate may be mentioned. Preferably, a polymer of methyl methacrylate and methyl methacrylate,
Polymer low monomer glass transition temperature, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid. Examples thereof include copolymers with lauryl.

The component (D) cross-links the components (A) and (B) during curing, and has the purpose of improving the curability, imparting toughness to the coating film, improving chemical resistance, etc. Used in. If the added amount of the component (D) is too large, the flexibility of the cured product deteriorates, so the content of the component (D) in the total 100 parts by weight of the components (A) to (D) is 0.1 to 10 parts by weight. It is preferably about the same.

As the component (D), ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di ( Alkanediol di (meth) acrylates such as (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth)
Polyoxyalkylene glycol di (meth) acrylate such as acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate,
Examples thereof include diallyl fumarate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. These may be used alone or in combination of two or more.

The paraffin wax as the component (E) transfers to the coating film surface during coating film formation and plays a role of blocking air during the curing reaction.

When the temperature in the summer is about 40 ° C., the surface temperature of the asphalt road rises to about 60 ° C., but since the syrup temperature before coating is 40 ° C., the coating temperature during coating is in the middle. It will be about 50 ° C.

The paraffin wax having a melting point of 68 to 80 ° C. used in the present invention forms a paraffin wax layer capable of blocking air under such temperature conditions to achieve normal curing of the syrup composition. One or more components in the temperature range are added in an amount of 0.15 to 1.0 part by weight based on 100 parts by weight of the components (A) to (D) in total.

Incidentally, in order to make the syrup composition curable (that is, usable) even at a temperature of about 20 to 35 ° C., paraffin wax having a melting point of 47 to 67 ° C. can be used together if necessary. .. In this case, the mixing ratio of the paraffin waxes having both melting points (ranges) can be appropriately changed according to the purpose of use, but the total addition amount is 0.4 with respect to 100 parts by weight of the components (A) to (D) in total. It is about 2.0 parts by weight.

As the paraffin wax having a melting point of 68 to 80 ° C., for example, paraffin wax HNP-9 (melting point 75 ° C.) and HNP-10 (75 of the same) manufactured by Nippon Seiro Co., Ltd. are used.
℃), 155 (69 ° C. in the same), microcrystalline wax Hi-Mic-2065 (75 ° C. in the same), Hi-Mi
c-1070 (79 ° C.) and the melting point of 47 to 67.
Examples of the paraffin wax at ℃ include paraffin wax 150 (melting point: 66 ° C.) manufactured by Nippon Seiro Co., Ltd., 13
5 (58 ° C. same), 125 (53 ° C. same), 115 (47 same)
C.) and SP-0145 (at 63.degree. C.) and the like.

The polymerization inhibitor of the component (F) has a storage stability,
Used for adjusting the curing speed. Specifically, hydroquinone, monomethoxy-hydroquinone, 2,6-
Di-t-butyl-P-cresol, 2-t-butyl-P
-Cresol and the like can be mentioned, but from the viewpoint of easy control of the addition amount, the latter two are preferably used because the addition effect is mild. The addition amount of the polymerization inhibitor is 1 in total of the components (A) to (D).
It is preferably 0.001 to 0.2 parts by weight with respect to 00 parts by weight.

The syrup composition of the present invention comprises the above (A) to
An inorganic filler such as calcium carbonate, alumina, silica, zinc white, or glass beads may be added to the component (F).

10 to 10 parts by weight of the inorganic filler having an average particle size of 100 μm or less based on 100 parts by weight of the components (A) to (F) in total.
By adding about 400 parts by weight, the curability of the coating film surface can be improved. Generally, it is preferable to add a small amount when the particle size is small, and to add a large amount when the particle size is large.

The syrup composition of the present invention can be cured by a redox catalyst comprising a combination of a curing agent and a curing accelerator.

An organic peroxide such as benzoyl peroxide or methyl ethyl ketone peroxide is used as a curing agent, and the addition amount is about 0.1 to 10 parts by weight per 100 parts by weight of the syrup composition.

Examples of the curing accelerator include cobalt salts such as cobalt naphthenate and cobalt octenoate, and aromatic tertiary amines. These cobalt salts and aromatic tertiary amines may be used alone or in combination. Examples of the aromatic tertiary amine include N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N-dimethylanisidine, N, N-diethylanisidine and N, N-dimethyl. -P-chloroaniline, N, N-dimethylaminobenzaldehyde, N,
N-di (hydroxyethyl) -P-toluidine, N, N
-Di (2-hydroxypropyl) -P-toluidine,
N, N-di (hydroxyethyl) aniline, N, N-di (2-hydroxypropyl) aniline and the like are used. Of these, N, N-di (hydroxyethyl) -P-toluidine, N, N-di (2-hydroxypropyl) -P
-Toluidine, N, N-di (hydroxyethyl) aniline and N, N-di (2-hydroxypropyl) aniline are preferable, and 0.2 to 0 is used with respect to 100 parts by weight in total of the components (A) to (D). It is used in the range of about 6 parts by weight.

When the amount of the curing accelerator is more than 0.6 part by weight, a large amount of radicals are generated at once at a coating temperature of 50 ° C. and the maximum exothermic temperature becomes high. Therefore, a polymer having a lower molecular weight than that at a temperature of 20 to 35 ° C. Tend to be produced, the physical properties become low tensile strength, and the amount of residual monomer tends to increase.

When the amount of the curing accelerator is less than 0.2 parts by weight, the amount of radicals generated is small, the heat generation is small, and the radical reaction does not proceed, resulting in poor curing.

These curing agents and curing accelerators are usually added to and mixed with the syrup composition immediately before the curing reaction such as coating operation. However, when an aromatic tertiary amine is used as the curing accelerator, it is not used by itself. Since the curing reaction does not proceed, it can be added to the syrup composition in advance and mixed for storage.

[0028]

EXAMPLES Examples will be described below.

Example 1 Methyl methacrylate 32 parts 2-Ethylhexyl acrylate 26 parts Methoxy polyethylene glycol # 230 methacrylate 10 parts (NK ester M-40G manufactured by Shin-Nakamura Chemical Co., Ltd.) Triethylene glycol dimethacrylate 2 parts N, N-di (2-hydroxypropyl) -P-toluidine 0.3 parts 2,6-di-t-butyl-P-cresol 0.05 parts Paraffin wax melting point 74 to 76 ° C 0.3 parts 〃〃65 ~ 68 ° C 0.3 parts 〃〃 54-57 ° C 0.3 parts mixture was charged into a 1 liter flask equipped with a stirrer, a thermometer, and a cooling pipe, and methyl methacrylate (MM
A) and n-butyl acrylate (BMA) copolymer (M
MA / BMA = 60/40, weight average molecular weight 42,000
0) 30 parts was added in small portions. Then, these mixtures were heated to 60 ° C. in a water bath. MMA / BMA
After the copolymer and paraffin wax were completely dissolved, the mixture was cooled. Thus, a composition having a viscosity at 20 ° C. of about 450 cps was obtained.

To 100 parts of this composition, 1 part of benzoyl peroxide powder (hereinafter abbreviated as BPO powder) having a purity of 50% was added as a curing agent under the conditions of 50 ° C. (both composition, base temperature, and ambient temperature of 50 ° C.). When it was mixed well and applied on a PET film to a thickness of 2 mm, it showed a maximum exothermic peak in 20 minutes, and a normal cured product was obtained. This cured product is JIS
Tensile test according to K6301 shows a breaking strength of 54
It showed kg / cm ² and a breaking elongation of 170%.

Further, to 100 parts of this composition, 3 parts of BPO powder was added as a curing agent under the conditions of 20 ° C. (both composition, base temperature, and ambient temperature of 20 ° C.) and mixed well to obtain PE.
When applied to a thickness of about 2 mm on the T film, it showed a maximum exothermic peak in 45 minutes, and a normal cured product was obtained. A tensile test of this cured product according to JIS K6301 revealed a breaking strength of 55 kg / cm ² and a breaking elongation of 181%.

(Example 2) Methyl methacrylate (MMA) 40 parts 2-Ethylhexyl acrylate (2-EHA) 26 parts Triethylene glycol dimethacrylate 2 parts N, N-di (2-hydroxypropyl) -P-toluidine 0.3 part 2,6-di-t-butyl-P-cresol 0.04 part Paraffin wax melting point 74-76 ° C 0.2 part 〃 〃 65-68 ° C 0.4 part 〃 〃 54-57 ° C 0. 5 parts of the mixture was charged into a 1-liter flask equipped with a stirrer, a thermometer, and a cooling tube, and while stirring, a copolymer of MMA / BMA (MMA / BMA = 60/40, weight average molecular weight 42,
000) 30 parts was added little by little. Then, these mixtures were heated to 60 ° C. in a water bath. MMA / B
After the MA copolymer and paraffin wax were completely dissolved, the mixture was cooled. Thus, a composition having a viscosity at 20 ° C. of about 400 cps was obtained. MMA of this composition
The weight ratio of monomer to 2-EHA monomer is 60/40.

To 100 parts of this composition, 1 part of BPO powder was added as a curing agent at 50 ° C. and mixed well to prepare 2 parts.
When it was applied to a thickness of mm, it showed a maximum exothermic peak in 18 minutes and was cured normally. This cured product has a breaking strength of 116 kg.
/ Cm ² and elongation at break 76%.

In addition, 100 parts of this composition was added to BPO.
When 1 part of powder and 250 parts of ceramic aggregate having a particle size of 0.5 to 1.0 mm were mixed well and troweled on a PET film at a temperature of 50 ° C. to a thickness of 3 mm, the maximum exothermic peak was shown in 22 minutes Cured.

Example 3 Methyl methacrylate 36 parts 2-Ethylhexyl acrylate 24 parts Phenoxy polyethylene glycol acrylate (n≈4) 7 parts (Aronix M-102 manufactured by Toagosei Kagaku Kogyo Co., Ltd.) Triethylene glycol dimethacrylate 2 parts N, N-di (2-hydroxypropyl) -P-toluidine 0.3 parts 2,6-di-t-butyl-P-cresol 0.04 parts Paraffin wax melting point 74-76 ° C 0.2 parts 〃 A mixture of 〃 65 to 67 ° C 0.4 part 〃 〃 54 to 57 ° C 0.5 part was charged into a 1-liter flask equipped with a stirrer, a thermometer, and a cooling tube, and methyl methacrylate (MM
A) and n-butyl acrylate (BMA) copolymer (M
MA / BMA = 60/40, weight average molecular weight 42,000
0) 30 parts was added in small portions. Next, these mixtures were heated to 60 ° C. in a water bath, and after the MMA / BMA copolymer and paraffin wax were completely dissolved, the mixtures were cooled. Thus, a composition having a viscosity of about 470 cps at 20 ° C. was obtained.

To 100 parts of this composition, 1 part of BPO powder was added as a curing agent at 50 ° C., mixed well, and mixed with P
When it was applied on the ET film to a thickness of 2 mm, it showed a maximum exothermic peak in 16 minutes, and a normal cured product was obtained. This cured product had a breaking strength of 99 kg / cm ² and a breaking elongation of 136%.

Further, 100 parts of this composition was added to BPO.
When 1 part of powder and 240 parts of ceramic aggregate having a particle size of 1.0 to 0.5 mm (Cerasand B particles manufactured by Bishu Kosan Co., Ltd.) were mixed well and applied to a PET film at a thickness of 3 mm at 50 ° C., it took 21 minutes. Showed the maximum exothermic peak, and a normal cured product was obtained.

(Example 4) 33 parts of MMA, 2-EHA
To 33 parts, and otherwise 20 ° C. in the same manner as in Example 2.
A composition having a viscosity of about 460 cps was obtained.

To this composition, 100 parts of SL-700 (calcium carbonate having an average particle diameter of 4.5 μm) manufactured by Takehara Chemical Industry Co., Ltd. was stirred with a high speed disperser to obtain a compound having a viscosity of 7000 cps at 20 ° C. It was

When 1 part of BPO powder was added to this composition at 50 ° C., mixed well and applied on a PET film to a thickness of 2 mm, a maximum exothermic peak was exhibited in 17 minutes, and a normal cured product was obtained.

Comparative Example 1 0.5 parts of a paraffin wax having a melting point of 65 to 68 ° C. and 0.5 part of a melting point of 54 to 57 ° C. were used.
A composition having a viscosity at 0 ° C. of about 450 cps was obtained.

To this composition, 1 part of BPO powder was added as a curing agent at 50 ° C., mixed well, and applied on a PET film to a thickness of 2 mm. The maximum exothermic peak was 18 minutes, but the coating film surface was "sticky", the coating film was softer than usual, and a normal cured product was not obtained.

(Comparative Example 2) N, N-di (2-hydroxypropyl) -P-toluidine was 1.0 part, and otherwise the same as in Example 1 except that the viscosity was about 420c at 20 ° C.
A ps composition was obtained.

B was added to this composition as a curing agent at 50 ° C.
1 part of PO powder was added, mixed well and applied on a PET film to a thickness of 2 mm. The maximum exothermic peak was 11 minutes, but the surface of the coating film was "sticky", the coating film was extremely soft, and a normal coating film could not be obtained.

[0045]

EFFECT OF THE INVENTION The syrup composition of the present invention has excellent curability at high temperatures, and can be applied even in air having a base surface temperature of about 35 to 60 ° C.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 191/08 PCZ 6770-4J C09J 4/06 JBN 7242-4J E04F 13/02 A 8913-2E 15 / 12 A 7805-2E

Claims (4)

[Claims] 1. A (meth) acrylic acid alkyl ester (A), an alkoxy (poly) alkylene glycol (meth) acrylic acid ester and / or an alkylphenoxy (poly) alkylene glycol (meth) represented by the following general formula.
Acrylic ester (B), (Meth) acrylic acid alkyl ester (co) polymer (C) soluble in the above (A) and (B), having two or more polymerizable double bonds in the molecule A syrup composition comprising a monomer (D), a paraffin wax (E) having a melting point of 68 to 80 ° C., and a polymerization inhibitor (F). [Chemical 1] (However, R ₁ is H or CH ₃ , R ₂ is an alkylene group, R
₃ is an alkyl group or an alkylphenyl group, n is 1 to 40
Is an integer. ) 2. The content of component (B) is zero.
The syrup composition described. 3. The syrup composition according to claim 1, further comprising an aromatic tertiary amine. 4. The syrup composition according to claim 1, further comprising an inorganic filler.