JPS58171430A - Primer composition for acryl modified urethane sealant - Google Patents

Abstract

PURPOSE:The titled composition having improved adhesiveness to Portland cement mortar, etc., comprising a mixture of a copolymer obtained from (meth) acrylonitrile, (meth)acrylic acid derivative, etc. and a silane coupling agent as a main component. CONSTITUTION:The desired composition comprising a mixture of (A) a copolymer obtained by copolymerizing a monomer mixture consisting of >=70wt% (i) (meth)acrylonitrile, (ii) methacrylate compound shown by the formula I (R<1> is 1-4C alkyl), (iii) a styrenic derivative shown by the formula II (n is number of methyl groups in benzene ring and 1-3), and (iv) a compound shown by the formula III (R<2> is H or CH3; X is COOH, group shown by the formula IV, CONH2, etc.) and (B) <=20wt% silane coupling agent based on the copolymer as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fryer composition for an acrylic modified urethane sealant.

In recent years, technological advances and diversification of needs in the construction industry have been remarkable, and the Japanese Industrial Standard J
Engineering SA 5758-1979 was also revised to include 9030.8020.7020.7010 and 70 as durability categories.
051! Five types of sealants have been defined, and polyurethane sealants can now be applied to 9030 durability sealants. However, conventional polyurethane sealants lack heat resistance, and in reality, polyurethane sealants that have undergone acrylic modification have the highest JISA! '1758-
It can be said that it meets the 1979 durability classification.

According to the present invention, the acrylic modified urethane sealant material has various advantages and is therefore practical? Despite this, acrylic modified urethane resin, which is the same type as the sealant, is commonly used as a primer when applying the sealant, and it is not always possible to immediately respond to requests. The present invention was arrived at as a result of extensive research and attention to the fact that it is not being used.

In other words, as a primer for a sealant, it is generally considered that a primer of the same type as a bed sheet is suitable, as long as its adhesion with the sealant is taken into account. teeth,
K for each target material (material to be sealed) within a limited range of conditions that does not expose the general drawbacks of urethane resin, such as poor heat resistance and easy photodeterioration.
A: Favorable conditions must be set, and a high degree of skill is required. From this point of view, the present inventors have attempted to provide a glimer composition for sealants that is fully applicable to acrylic modified urethane sealants without incorporating a urethane resin. b) It means an acrylonitrile or methacrylonitrile 1-4 alkyl group. ) is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus. ), and -(CH OH (an integer of 2 to 4 for sea bream) or 00-Y
(Y Id NHx , Nu(:H!OR”(R”
d H5L11 alkyl group having 1 to 4 carbon atoms) or (CH
I) J-N(R')! (l is an integer of 1 to 4; R4 is an alkyl group having 1 to 4 carbon atoms); A copolymer obtained by copolymerizing a heptamer alloy containing 70 weight or more of the compound involved in ] and a silane coupling agent in an amount equivalent to 20 weight or less of the copolymer. Ply composition for 2-piece acrylic modified urethane sheet as a component (1) A) Acrylonitrile μ or methacryl tetranitrile means a furkyl group having a formula value of 1 to 4. j).

In the methacrylate compound represented by, X is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus. ) Styrene derivatives represented by -(CH
(Y NHHz, NHCHOR" (R3H or C alkyl group having 1 to 4 carbon atoms) or (Cut).

-NCR')z (l is an integer of 1 to 4; R4 represents an alkyl group having 1 to 4 carbon atoms)). A copolymer obtained by copolymerizing a heptamer mixture containing 70 weight or more of a compound represented by the following: and e) triaryl isocyanuric acid; and a silane cup in an amount equivalent to 20 weight or less of the copolymer. A primer composition for an acrylic modified urethane sealant containing a mixture with a ring agent as a main component, and (i) acrylonitrium μ or metaacrylonitrile 1 to
4 means an alkyl group. ) is an integer from 1 to S indicating the number of methyl groups substituted on the benzene nucleus. ) Styrene derivatives represented by 1 2) General formula 〇H鵞=δ−X [In the formula, R3 is H or methyl
(CH snow) = -on (solution is an integer from 2 to 4) or Co
-Y (Y haNH*, NT(CH!OR) (R
"a H or a furkyl group having 1 to 4 carbon atoms) also 0 old 1
-N(R')* (l is an integer of 1 to 4, R4 is a furkyl group having 1 to 4 carbon atoms)'). ], e) triallylin cyanuric acid, and S, to) general formula CH2=Z-Z-Si (OR@) [wherein 2 is (CHsp or ij CO-(CHl)q (
/1 is an integer of 1 to 4 (9f is an integer of 1 to 10), R1 is H or a methyl group, and R6 is an aykiμ group having 1 to 100 carbon atoms. ] The main component is a mixture of a copolymer obtained by copolymerizing a monomer mixture containing 70 weight or more of the silane compound represented by the following; and a silane coupling agent in an amount corresponding to 20 weight or less of the copolymer; A primer composition for an acrylic modified urethane sealant is provided. In this article, the compounds of 2), more specifically, acrylic acid, methazolyl acid, and their derivatives, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyglobyl acrylate, and hydroxybutylacrylate.

Hydroxyethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc., or hydroxyl methacrylate, acrylic acid, methacrylic acid, N-
Methyl-μacrylic acid, N-methylo-methacrylic acid, their derivatives, N-methoxymethylacrylic acid, N-ethoxymethylacrylic acid.

Acrylamide, N-butoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, N-
Glopoxymethylmethacrylamide, N-alkoxymethylacrylamide such as N-butoxymethylmethacrylic acid, dimethylmethacrylic acid in N-alcohol, glycidyl acrylate, glycidyl methacrylate, etc., and these Among them, 2-Hydenoxyethyl Methacrylate Co., Ltd., in particular, showed good results in the water resistance test described below.

Specifically, the silane compound in (g) is γ-acyclooxyglobyltrimethoxysilane.

γ-acrypoxypbi and triethoxysilane.

γ-Acycloxyglobil triglopoxicin.

T-acryloxyg p-v tributoxycin.

γ-Metacycloxypropyltrismethoxyethoxysilane, r-methacryloxypropyltrisethoxyethoxysilane, r-methacryloxypropyltrimethoxysilane, γ-metacycloxyg4-triethoxysilane, r-methacryloxyglobi-tributylsilane, δ
- Lists methacryloxybutyltrimethoxysilane, trimethoxyvinylsilane, and triethoxyvinylsilane.
'le can.

(A) 9), No. 9 above. When mixing the compounds corresponding to →, e), f) to make a mono-oh mixture,
Select one or more compounds corresponding to (1), -), →, (e), and (e), respectively, and hereinafter, the compounds or compound groups selected in this manner will be referred to using the codes to which they belong. ingredient, mouth) ingredient, c) ingredient, 2) ingredient, e) ingredient,
(expressed as components), according to the mixing ratio shown below.

That is, the mixing ratio of each component varies depending on the type of acrylic modified sealant to which the target primer is applied, so it cannot be determined unconditionally, but in general,
Component (a) is mixed in such a way that it accounts for 10 to 40% by weight, preferably 15 to 50% by weight of the total monomers; 60% by weight, 8) component 2 to 30% by weight, preferably 5 to 20% by weight, 2) component 5 to 40% by weight,
They are preferably mixed in an amount of 5 to 30% by weight.

In addition, the total amount of component (e) to component (i) to component (ii) is 10
0 parts by weight, add an amount not exceeding 100 parts by weight, preferably 50 parts by weight or less, and similarly when adding component (a), to 100 parts by weight of the total amount of components a) to → components, Add in an amount not exceeding 100 parts by weight, preferably not more than 50 parts by weight.

b) If the amount of the component is too small, the heat resistance, hot water resistance, and oil resistance will be insufficient; if the amount is too large, the weather resistance and normal adhesion will be insufficient.

In addition, if the amount of component (1) is too small or too large, the normal adhesiveness will be insufficient. C.) If the amount of the component is too low, heat resistance and boiling water resistance will be affected, while if it is too high, the oil resistance will be affected.

If the normal state adhesion is insufficient, tb=>If the component is too small, the adhesion to the sealant will be insufficient, and if it is too large, the hot water resistance will be insufficient.

Addition of component e) and component f) is effective in improving the adhesion and hot water resistance of the target object, but if the amount of both components e) is too large, gelation may occur during copolymer synthesis. Second, the solution viscosity of the copolymer increases, resulting in a decrease in workability and also in the normal state adhesion of the target object. On the other hand, if the amount of the latter component is too large, the affinity for the target sealant will decrease and the adhesiveness will also tend to decrease.

b) To) Monomers other than the components should not be added if possible, but include ethylene, propylene, and butene.

Alkylene compounds such as butadiene, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate.

Long chain alkyl methacrylates such as stearyl methacrylate, vinyl compounds such as vinyl acetate, vinyl propionate, vinyl chloride, maleic acid.

Unsaturated carboxylic acids such as fumaric acid, itaconic acid and esters thereof may be allowed in amounts not exceeding 3031 of the total monomers.

To prepare the sealant primer composition of the present invention, the monomers mixed as described above are first subjected to bulk polymerization, solution polymerization, and the like in the presence of heat, light, electron beams, or a catalyst such as peroxide. A copolymer is produced by gas phase polymerization or emulsion polymerization,
Next, a silane coupling agent is added to the copolymer in an amount of 201% by weight or more, preferably 01 to 101 to 10% by weight, and the mixture thus obtained is dissolved in a suitable organic solvent to form a solution with a suitable viscosity. do it.

Addition of the above-mentioned silane coupling agent is effective in improving the adhesion, cold resistance, and hot water resistance of the target object, but if the amount added is too large, the adhesion (softness) will decrease. Examples of silane coupling agents include mercaptosilane. Examples include aminosilane and epoxysilane. Solution polymerization is the most advantageous method for monomer polymerization, as it allows the organic solvent used during polymerization to remain in the final product without being removed.

For solution polymerization, for example, benzoyl peroxide,
t-Butyl peroxide, lauroy, 1/peroxide, methyl ethyl ketone peroxide.

A commonly used polymerization initiator such as cumene peroxide, dicumene oxide, dicumene hydroperoxide, azobisisobutyronitrile, etc.
It may be used in a ratio of 0.05 to 5 parts by weight based on 100 parts by weight of the monomer. Busy α05~10]1[
It can be used in a proportion of 1 part.

The solvent used in solution polymerization may be any solvent as long as it dissolves the copolymer, but alcohols, amines, etc. having active water volume should preferably be avoided. - The copolymer thus obtained is good if it exhibits an intrinsic viscosity [η]K of α07 to α50 all in a DMF solution at 30'C, 11 to 0.5 de/I by 9 parts, The lower the intrinsic viscosity, the lower the adhesiveness and heat resistance.
On the other hand, if the diameter is too large, the adhesion will decrease and the workability will also deteriorate.

Finally, the sealant primer of the present invention has a solution viscosity of 2000p9 or less, preferably 10p9 or less in the environment in which it is used.
The copolymer and silane coupling agent are provided by dissolving them in a suitable solvent so that the concentration is 0Q'p9 or less, and the same solvent as the solvent for solution polymerization may be used as the solvent at this time. In addition, commonly used additives such as colorants, viscosity modifiers, storage stability improvers, etc. can be used in combination with the sheet primer.

As is clear from the above, the present invention provides a primer composition that can be applied to Acry V modified urethane sealant without incorporating a urethane resin, and is suitable for use with cement mortar, where adhesion is most likely to be a problem. When used as a target material, it exhibits good performance over a relatively wide composition range, as shown in the Examples and Test Examples described below.

Hereinafter, the present invention will be explained in more detail with reference to copolymer production examples, examples, test examples, etc.

Copolymer production example 1 20 parts of acrylonitrile, butyl methacrylate) 45
parts, 10 parts of styrene, 25 parts of 2-hydroxyethyl methacrylate, and 75 parts of toluene.

and 25 parts of acetone were mixed uniformly, 3 parts of azobisin butyronitrile was added thereto, and heated under stirring and reflux for 15 hours while maintaining the liquid temperature at 85°C, and the non-volatile content was 49.
A 5% colorless and transparent copolymer solution was obtained. This copolymer was precipitated with petroleum benzene, separated in a furnace, dried under reduced pressure at room temperature, and its limiting viscosity at 50°C was determined with dimethyl formaldehyde, which was 9 and α258.

Copolymer production example 17 Acrylonitrile A/20 parts, butyl methacrylate 4
5 parts, 10 parts of styrene, 25 parts of 2-hydroxyethyl methacrylate, 10 parts of triallylisocyanuric acid,
)71/engine and 30 parts of acetone were uniformly mixed, 3 parts of azobisin butyronitrile was added thereto, and the mixture was heated for 18 hours while stirring and refluxing while keeping the liquid temperature at 80°C. A colorless and transparent copolymerization solution with a non-volatile content of -49.0% was obtained. NP of this copolymer! The viscosity was measured in the same manner as in Production Example 1 and was found to be α289.

Copolymer production example: 25 parts of acrylonitrile, 50 parts of butyl methacrylate per day
parts, 10 parts of styrene, 15 parts of 2-hydroxyCtiV methacrylate, 25 parts of triallylisocyanuric acid, γ-
20 parts of methoxypropyltrimethoxysilane, 100 parts of toluene.

and 45 parts of acetone were uniformly mixed, 3.5 parts of azobisisobutyronitrile A was added thereto, and the mixture was heated for 18 hours with stirring and reflux while maintaining the liquid temperature at 80°C.
A colorless and transparent copolymer solution of J4a5- was obtained.

This copolymer was precipitated with petroleum benzine, diluted with a small amount of acetone, precipitated again with petroleum benzine, separated in a furnace, dried under reduced pressure at room temperature, and the viscosity at 50°C was determined using dimethyl formand. Roα26
1 and nine.

Copolymer production examples 2 to 16, 19 to 32 mono! A copolymer of the present invention and a copolymer for comparison were obtained in the same manner as in the above production example except that the type and amount of - were changed.

The types and amounts of monomers and the intrinsic viscosity [η] of the produced copolymers in these production examples are as in Production Example 1 and Production Example 17.
．． 9 is shown in Table 1 along with the case of Production Example 18.

Examples and Comparative Examples Toluene was added to the toene-acetone solution of the copolymer obtained in the above production example so that the concentration of the copolymer was 30%,
Next, a silane coupling agent was added to the 50-solution of this copolymer and mixed uniformly to obtain a primer composition of the present invention and a ninth primer composition for comparison. The above is shown in Table 2.

In addition, trimethoxymercaptopropylsilane in Table 2 is
Product manufactured by Tone Silicone Co., Ltd. [5H6062J
The trimethoxyglycidoxyethylsilane is the company's product rsH6040J.

Test Example The following tests were conducted using the sealant glimer compositions obtained in the above Examples and Comparative Examples.

The results are shown in Table 3.

Adhesion test> A primer composition was applied to each side of two cement mortar blocks measuring 50 x 50 ff x 25111 prepared in accordance with Section 5.12.2 of JISA 5758, and left at room temperature for 50 minutes. In accordance with Section 5.12.5 of JISA 5758, top sealer Au (manufactured by Yamauchi Rubber Industries Co., Ltd., trade name) was applied to the center using a spacer.

50MK x 12 by extruding acrylic modified sealant)
A column of 12M of cod was adhered to the cement mortar and cured, and cured at room temperature for 7 days and then at 50°C for 7 days to prepare a test piece for a tensile adhesion test. Using three test pieces thus obtained, the cohesive failure rate and tensile adhesive strength were measured using a tensile tester.

<Hot Water Resistance Test> Three test pieces prepared in the same manner as in the adhesion test were immersed in warm water at 50°C for two days, and then a tensile test was conducted in the same manner as in the adhesion test.

<Heat resistance test> Using three test pieces prepared in the same way as the adhesion test, JISA
According to Section 5.12.3 of 5758, 80℃ or 90℃
After heating for 14 days, a tensile test similar to the adhesion test was conducted.

<Durability test> Using 5 test pieces prepared in the same way as the adhesion test, JISA
The durability test (durability categories 8020 and 9050) according to Section 5.12.3 of 5758 was completed.

In Table 3, OF is the cohesive value tS < fracture at the sealant part, TL is the thin wave jJl (fracture at the boundary between the sealant and primer), and AF is the interface fracture (fracture between the primer and the target material). ) respectively, and the numbers after OF, TL, and AF are characterized by the area ratio.Patent Applicant: Yamauchi Rubber Industry Co., Ltd. Representative Patent Attorney: Kanji Ida Continued from Page 1 0 Inventor: Yoshikazu Nakayama Hachijo, Nagaokakyo City Gaoka 2-1 Ichiban-1 Building 1 503

Claims (1)

[Claims] ①, ①) acrylonitrile ~ or methacryltetranitrile ♂ ~ 4 refers to the aμ group. ), where n is an integer from 1 to 5 indicating the number of methacrylate groups substituted on the benzene nucleus. ) Styrene derivatives represented by
and 8 2) General formula OH value = b-x In the C formula, R3 is H or methi (CH means OH (# is an integer from 2 to 40) or C0-Y
The printing is NH (CHI), NH (] oR" (f is H-shaped carbon number 1 to 4 oy u* u group), and 1d (CHI)z-
N(R')*(l is an integer of 1 to 4 R4 is a carbon number of 1 to 4
means the aμ group)). Acrylic whose main component is a mixture of a copolymer obtained by copolymerizing a monomer mixture containing 70% by weight or more of the compound represented by ] and a silane coupling agent in an amount equivalent to 0.20% by weight or less. Primer composition for modified urethane sealant. ■、B) Acrylonitrile μ or metaacrylonitrile μ～
4 means a monovalent alkyl group. ) is a methacrylate compound represented by 1, which means the number of methyl groups substituted on the benzene nucleus.
It is an integer of ~3. ) Styrene derivative represented by 3 2) General formula 〇H! =C-XC In the formula, R3 is H or methyl (CH--OH (m is an integer of 2 to 4) or C.-E (Y is NH!, NHCHtOR"(R" is H
or (CHI)7-N
(R')m (l is an integer of 1 to 4, R4 is an alkyl group having 1 to 4 carbon atoms)). A copolymer obtained by copolymerizing a monomer mixture containing 70 weight or more of a compound represented by the following: and e) triaryl-isocyanuric acid; and a silane coupling agent in an amount corresponding to 20 weight or less of the copolymer. A primer composition for acrylic-modified urethane sealants whose main component is a mixture of ■, a) Acrylonitrile or metaacrytetranitrile
It means an Aki μ group of 1 to 4. ) is an integer from 1 to 3 indicating the number of methyl groups substituted on the benzene nucleus. ), 2) a styrene derivative represented by the general formula cHz=b−X (wherein R″ is H or methyμ(
CH, -OH (# is an integer from 2 to 4) or C0-Y (
Y Ha NH Tomi, NHOH Yuki OR” (R”ij H or Haru i prime number 1 to 4 afit-JPN group) or (CHI)
J-N(Rj) (l is an integer of 1 to '4, R4 is an alkyl μ group having 1 to 4 carbon atoms)). ], e) triary-isocyanuric acid, and 1) general formula 〇H weight=δ-Z-8i, (OR) [in the formula 2
(CHz)l) Also, HaCo-(CHS, (Tosha 1 is an integer of 1 to 4, q is an integer of 1 to 10), RB is H or a methyl group, R6 is a fulky group with a carbon number of 1 to 100 ] A mixture of a copolymer obtained by copolymerizing a monomer mixture containing at least 70% by weight of a siler compound represented by the following; and a silane coupling agent in an amount corresponding to 20% by weight or less of the copolymer. A fryer composition for acrylic modified urethane sealants containing as the main component.