JPH09255938A - Primer composition for sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer compsn. for a sealing material which compsn. has a high transparency, a stable ultraviolet absorbing power over a long period of time, and good storage stability. SOLUTION: In this compsn. comprising a solid resin component such as a polyisocyanate and an org. solvent, 0.1-15wt.%, based on the solid resin component, at least one kind of fine metal oxide particles of at most 1,000nm in a maximum particle size, selected from among fine cerium oxide particles, fine zinc oxide particles and fine titanium oxide particles, are incorporated together with a sulfonic acid surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition for a sealing material, and more particularly to a sealing composition having a high transparency, a stable ultraviolet absorbing ability for a long period of time, and a good storage stability. It relates to a wood primer composition.

[0002]

2. Description of the Related Art In a sealing material applied to a translucent adherend such as glass, ultraviolet rays are radiated through the adherend, so that the sealing material on the adhesive surface gradually deteriorates. However, the adhesiveness is reduced.

Conventionally, as a method for suppressing the deterioration of the sealing material on the adhesive surface due to ultraviolet rays, a method of blocking ultraviolet rays at the primer portion has been proposed. Specifically, an organic type is used in the primer composition. A method of blending the ultraviolet absorber or pigment has been proposed.

However, a primer composition containing an organic ultraviolet absorber cannot obtain a stable ultraviolet absorbing ability for a long time because the ultraviolet absorber is deteriorated or volatilized by heat or light. Further, the primer composition made opaque with a pigment has a problem in that a portion that is applied beyond the portion where the sealing material is applied has a poor appearance and impairs the design.

[0005] In order to solve the above problems,
Previously, there was proposed a primer composition for a sealing material which contains cerium oxide fine particles as an ultraviolet absorber and has a high transparency and a stable ultraviolet absorbing ability for a long time (Japanese Patent Application No. 6-228853). Depending on the surface treatment agent for the cerium oxide fine particles, there is a drawback that the cerium oxide fine particles precipitate and solidify during storage.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a primer composition for a sealing material, which is highly transparent, has a stable UV absorbing ability for a long period of time, and has good storage stability. To do.

[0007]

As a result of earnest research in view of the above problems, the present inventors have found that (a) cerium oxide fine particles,
By blending at least one metal oxide of (b) zinc oxide fine particles and (c) titanium oxide fine particles and a sulfonate-based surfactant, it has high transparency and has stable ultraviolet absorbing ability for a long period of time. Moreover, it was discovered that a primer composition for a sealing material having good storage stability was obtained, and the present invention was obtained.

That is, the primer composition for a sealing material of the present invention comprises (1) (a) fine particles of cerium oxide, (b) fine particles of zinc oxide and (iii) a composition containing a solid resin component and an organic solvent. ) A primer for a sealing material, which contains 0.1 to 15% by weight (based on a solid resin component) of at least one metal oxide fine particle of titanium oxide fine particle and (2) a sulfonate-based surfactant. The present invention relates to a composition.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. (A) Solid resin component The solid resin component of the primer composition for a sealing material is preferably polyisocyanate. Such polyisocyanate is a monomer or multimer (for example, oligomer) of polyisocyanate which is usually a raw material of polyurethane, and specifically, tolylene diisocyanate, diphenylmethane diisocyanate, poly Methylene polyphenyl isocyanate (Crude MDI), hexamethylene diisocyanate, isophorone diisocyanate,
Examples include xylylene diisocyanate and multimers thereof. (B) Metal oxide fine particles (a) Cerium oxide fine particles, (b) Zinc oxide fine particles,
(C) The maximum particle diameter of the metal oxide fine particles of the titanium oxide fine particles is usually 1,000 nm or less, preferably 30.
It is 0 nm or less, and more preferably 100 nm or less. When the maximum particle size exceeds 1,000 nm, the individual particles become heavy, so that a low viscosity liquid such as a primer composition for a sealing material has poor dispersibility of the metal oxide fine particles, and The transparency of the particles of the
Transparency is reduced.

In the present invention, the maximum particle size of the metal oxide fine particles is measured by a particle size distribution meter according to the laser-type dynamic light scattering method. Examples of such a measuring device include a submicron particle sizer (manufactured by Nicomp Co., Ltd.) and a dynamic light scattering photometer (manufactured by Otsuka Electronics Co., Ltd.).

The metal oxide fine particles (a) cerium oxide fine particles, (b) zinc oxide fine particles, and (c) titanium oxide fine particles are mixed in the solid resin component (polyisocyanate) constituting the primer composition for a sealing material. -G), etc., usually 0.1 to 15 parts by weight, preferably 0.1.
2 to 10 parts by weight. Since the primer layer applied to the adherend is very thin, if it is less than 0.1 parts by weight, sufficient ultraviolet light absorption ability cannot be imparted. On the other hand, if the amount exceeds 15 parts by weight, the adhesion performance of the primer composition deteriorates, which is not preferable. (C) Sulfonate-based surfactant (b) A sulfonate-based surfactant is blended as a dispersant for (b) metal fine particles in an organic solvent, or surface-treated with a sulfonate-based surfactant in advance (b) The same effect can be obtained by adding fine metal particles. Examples of the sulfonate surfactant include sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and the like.
(B) The metal fine particles are provided with a dispersibility in an organic solvent.
The lower limit of the blending amount of the sulfonate-based surfactant is 1 part by weight or more, and preferably 5 parts by weight or more based on 100 parts by weight of the (b) metal fine particles. When the amount is less than 1 part by weight, the effect of imparting sufficient dispersibility of the metal fine particles (b) to the organic solvent is poor, and thus it is not preferable. The upper limit of the amount of the sulfonate-based surfactant compounded is 10 parts by weight or less, preferably 100 parts by weight of the solid resin component (polyisocyanate or the like) constituting the primer composition for a sealing material, and preferably It is 5 parts by weight or less. If it exceeds 10 parts by weight, the adhesion performance of the primer composition is deteriorated, which is not preferable. (D) Silane Coupling Agent The primer composition usually contains a silane coupling agent in order to improve the adhesiveness of the sealing material. As such a silane coupling agent, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) -silane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ -(Β-aminoethyl)
Aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like can be mentioned. To be

The amount of such a silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the solid resin component. If the blending amount is less than 0.1 parts by weight, the adhesion-imparting effect is poor, and if it exceeds 30 parts by weight, the adhesion-imparting performance of the primer composition deteriorates, which is not preferable. (E) Organic solvent An organic solvent is added for the purpose of adjusting the viscosity of the primer composition and (b) dispersing the metal fine particles.
Examples of such an organic solvent include methyl ethyl ketone, toluene, methyl isobutyl ketone, xylene, ethyl acetate, butyl acetate, and the like, and the sulfonate surfactant is particularly compatible with methyl ethyl ketone, toluene, methyl isobutyl ketone, and xylene. Is good. The compounding amount of the organic solvent is 3 parts by weight with the solid resin component being 100 parts by weight.
0 to 300 parts by weight is preferable, and more preferably 50 to 2 parts.
00 parts. When the blending amount of the organic solvent is less than 30 parts by weight, the coating layer of the primer composition becomes thick and becomes brittle,
If it exceeds 300 parts by weight, the adhesive performance of the primer composition will be deteriorated, which is not preferable.

The primer composition for a sealing material of the present invention is particularly suitable for use as a primer for a polysulfide sealing material. As such a polysulfide sealing material, (A) a polymer containing two or more thiol groups in one molecule, (B) a curing agent, and (C) other additives as required. A curable composition formed by blending is included. These components will be described below. (A) Polymer containing two or more thiol groups in one molecule-Two or more thio groups in one molecule in the curable composition.
The polymer containing a group is-(R ₁ S _x ) n- (where x is an integer of 1 to 5, n is an integer of 1 to 50, R ₁
Is preferably a polymer containing a skeleton represented by an organic group having 1 to 12 carbon atoms, more preferably R ₁ in the skeleton is —CH ₂ CH ₂ —, —CH ₂ OCH ₂ —, —C ₂ H ₄ O
_{C 2 H 4 -, - C} 2 H 4 OCH 2 OC 2 H 4 -, - C 4
H ₈ OC ₄ H ₈ - like polymer is an alkylene group or an oxyalkylene group -, and particularly preferably the general formula _{HS (R 1 S x) nR} 1 SH ( where, x is an integer of 1 to 5, n Is an integer from _{1 to} 50, R ₁
It is _{-CH 2 CH 2 -, - CH} 2 OCH 2 -, - C 2 H 4
_{OC 2 H 4 -, - C} 2 H 4 OCH 2 OC 2 H 4 -, - C
₄ H ₈ OC ₄ H ₈ — and other alkylene groups or oxyalkylene groups. ) Polysulfide polymer represented by
And / or (b) - (R ₂ O) m-(where, R ₂ is an alkylene group having 2 to 4 carbon atoms, m is an integer of 6 to 200) polyether represented by - and ether moiety, (b) -(C ₂ H ₂ OCH
_{2 OC 2 H 4 -S x)} -, and - (CH ₂ CH (OH)
CH ₂ —S _x ) — (where x is an integer of 1 to 5)
A structural unit represented by
_{-C 2 H 4 OCH 2 OC 2} H 4 -SH and / or -CH
₂ CH (OH) CH ₂ —SH is a polysulfide polyether polymer.

The molecular weight of the polysulfide polymer is preferably 100 to 200,000, more preferably 400 to 50,000. A preferred example of such a polysulfide polymer is US Pat.
No. 6,963.

Further, the polysulfide polyether polymer has ₂ to 95% by weight of-(R ₂ O) m-component of (a) and-(C ₂ H ₄ OCH ₂ OC ₂ H ₄ )-of (b). component is 3 to 70 _{wt%, - (CH 2 CH (} OH) CH 2) -
1 to 50% by weight of component, and polysulfide-bonded S _x
Is preferably 1 to 60% by weight, and in the polymer, the polyether moiety of (a) and the structural unit represented by (b) may be bonded in any sequence.

The polysulfide polyether polymer preferably has a number average molecular weight (Mn) of 600 to 200,
000, and more preferable number average molecular weight is 800-5.
It is 0000.

The polysulfide polyether polymer can be produced by a method described in, for example, JP-A-4-363325. (B) Curing agent The substances conventionally used as curing agents for thiol group-containing polymers can be used. Specific examples of these curing agents include ZnO ₂ , FeO ₂ , PbO ₂ , MgO ₂ , and CaO.
₂ , BaO ₂ , MnO ₂ , TeO ₂ , SeO ₂ , Pb ₃
Inorganic peroxides such as O ₄ , SrO ₂ and LiO ₂ , ZnO,
FeO, PbO, Fe ₂ O ₃ , Sb ₂ O ₃ , MgO, C
inorganic oxides such as oO, CaO, CuO, BaO, benzoylper-oxide, dicumylper-oxide, cumene hydroperoxide, t-butylhydroperoxide, t-butylperbenzoate, soda peracetic acid,
Organic peroxides such as urea peroxide, organic oxidants such as nitrobenzene, dinitrobenzene, paraquinone dioxime, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (curl) MDI), hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and other polyisocyanate monomers and their multimers, and active hydrogen-containing compounds containing the above polyisocyanate compound. Urethane prepolymers obtained by the reaction are mentioned, but among them, PbO ₂ is widely used.

The amount of these curing agents blended varies depending on the type of the curing agent, but is preferably 1 to 100 parts by weight per 100 parts by weight of the polymer containing two or more thiol groups in one molecule. It is more preferably 1 to 80 parts by weight. If the compounding amount is less than 1 part by weight, the curing will be incomplete, and
If it exceeds the weight part, the cured product becomes brittle, which is not preferable. (C) Other additives Further, a vulcanizing agent such as sulfur can be added to impart elasticity to the composition. Further, in order to improve economic efficiency, workability in applying the composition and physical properties after curing, fillers such as calcium carbonate, talc, clay titanium oxide and silica, phthalic acid ester, and butylbenzylphthalein are used.
(BBP), chlorinated paraffin, hydrogenated ta-phenyl and other plasticizers may be added.

[0019]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. [Synthesis Example 1] 1000 g of bifunctional polypropylene glycol (OH value 56.4 mg) obtained by adding propylene oxide to propylene glycol, 107 g of epichlorohydrin, and 1.25 g of second chloride Charge tin pentahydrate into a 2 liter reaction vessel and stir for 3 hours at 80-90 ° C.
Stirred for hours. Further, polysulfide polymer ("Thiocol LP55" manufactured by Toray Thiocol Ltd., mercaptan content 1.8% by weight, viscosity 450 poise (25
C.)) 1110 g were added and mixed, then 89.9 g of sodium hydrosulfide (purity 72.3%) was added, and the mixture was stirred at 80 ° C. for 2 hours. Then, the salt is removed, and the mercaptan content is 2.0.
A light yellow transparent polymer having a weight% and a viscosity of 80 poise (25 ° C.) was obtained. [Examples 1 to 8] Polyisocyanate (TDI trimer)
Body, HDI trimer body, and mixture of IPDI TMP adduct body) (solid resin component 80% by weight) 100 parts by weight (based on solid resin component), maximum particle size 50 nm (average particle size 8 nm) alkylbenzene sulfonic acid Sodium-treated cerium oxide fine particles (Taki Chemical Co., Ltd.
Le U-100 ″), maximum particle size 200 nm (average particle size 50
nm) untreated zinc oxide fine particles, maximum particle size 160
nm (average particle size 35 nm) of Al ₂ O ₃ + organosiloxane surface-treated titanium oxide fine particles, sulfonate-based surfactant, methyl ethyl ketone, toluene and silane coupling agent are mixed in a ratio shown in Table 1 and screwed. The sedimentation property of the metal oxide fine particles was evaluated by a method of observing after leaving the tube for 1 month or 6 months. Table 5 shows the evaluation results.

Further, the obtained primer composition was applied to a glass plate (50 × 50 × 5 mm), and JIS A-57 was used.
An H-type test body according to 58 was produced. The obtained H-type test body was mainly composed of polysulfide polymer "Thiocol LP55" manufactured by Toray Thiocol Co., Ltd., which was obtained by mixing a main agent, a curing agent and a coloring agent whose composition is shown in Tables 3 and 4. Polysulfide sealing material A as a component and polysulfide sealing material B having the polymer obtained in Synthesis Example 1 as a main component (only Example 1) were filled, and the temperature was 20 ° C. × 7 days + 50 ° C. ×
After the initial curing on the 7th, the sunshine weatherometer
Accelerated exposure was carried out with an accelerated exposure tester from 3,000 hours to 8,000 hours, and a tensile test was performed every 1,000 hours to observe the adhesive fracture state and evaluate the light resistance. Table 6 shows the evaluation results. [Comparative Examples 1 to 5] As shown in Table 2, the sulfonate-based surfactant was prepared in the same manner as in Examples 2 and 3 except that the amount of the sulfonate-based surfactant was 0.01 part by weight. In the same manner as in Example 4 except that the amount of the agent was not blended, the maximum particle size was 250 nm (average particle size) instead of the cerium oxide fine particles treated with sodium alkylbenzenesulfonate having a maximum particle size of 50 nm (average particle size 8 nm). (60 nm) fatty acid-treated cerium oxide fine particles 1 part by weight, except that the amount of the sulfonate-based surfactant was not blended in the same manner as in Example 1, and the maximum particle diameter was 200 nm (average particle diameter 50 n
A primer composition was prepared in the same manner as in Example 2 except that the maximum particle size of 150 nm (average particle size 30 nm) was changed to 1 part by weight instead of the unsurface-treated zinc oxide particles of m).
Using the obtained primer composition, the sedimentation property of the metal oxide fine particles was evaluated in the same manner as in Example 1. Table 5 shows the evaluation results. [Comparative Example 6] Example 1 except that the metal oxide fine particles and the sulfonate-based surfactant were not blended as shown in Table 2.
A primer composition was prepared in the same manner as in. Using the primer composition thus obtained, H-type test bodies filled with the polysulfide sealing materials A and B having the formulations shown in Tables 4 and 5 were prepared in the same manner as in Example 1, and the temperature was 20 ° C. × 7 days + 50 ° C. ×. 7
After the initial curing of the day, accelerated exposure from 3,000 hours to 8,000 hours was performed with a sunshine weatherometer accelerated exposure tester, and a tensile test was performed every 1,000 hours to observe the adhesive failure status. Then, the light resistance was evaluated. Table 6 shows the evaluation results. [Comparative Examples 7 and 8] Primer compositions were prepared in the same manner as in Examples 2 and 3 except that the amount of the sulfonate-based surfactant was changed to 15 parts by weight as shown in Table 2. According to the obtained primer composition, polysulfide sealing material A having the composition shown in Table 4 was prepared in the same manner as in Examples 2 and 3.
The H type test body filled with
* After initial curing for 7 days, accelerated exposure from 3,000 hours to 8,000 hours was performed using a sunshine weatherometer accelerated exposure tester, and a tensile test was performed every 1,000 hours to determine the adhesive failure status. Was observed and the light resistance was evaluated.
Table 6 shows the evaluation results.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6] As is clear from Table 4, the primer composition of the present invention has almost no settling of metal oxide fine particles even after storage, and therefore always maintains stable performance.

As is apparent from Table 5, the primer composition of the present invention can maintain the light resistance of the adhesive surface of the sealing material for a long period of time.

[0028]

EFFECT OF THE INVENTION The primer composition for a sealing material of the present invention has high transparency, has a stable ultraviolet light absorption ability for a long period of time, and has good storage stability. Since there is no sedimentation of metal oxide fine particles in the primer composition due to storage, stable performance is maintained, and when the sealing material is adhered to an adherend that transmits light, such as glass, it is previously applied. By applying it to the body, photo-deterioration of the sealing material is suppressed for a long period of time. Since the transparency is high, the design property around the sealing material is not lost even if the applied primer composition extends out of the sealing material.

Claims (7)

[Claims] 1. A composition containing a solid resin component and an organic solvent,
(1) 0.1 to 15% by weight (based on solid resin component) of at least one metal oxide fine particle selected from (a) cerium oxide fine particles, (b) zinc oxide fine particles, and (c) titanium oxide fine particles; and (2) sulfone. A primer composition for a sealing material, which comprises an acid salt-based surfactant. 2. The primer composition for a sealing material according to claim 1, wherein the sulfonate surfactant is contained in the resin by the surface treatment of the metal oxide fine particles in advance. 3. A primer for a sealing material according to claim 1 or 2, further comprising a silane coupling agent.
Composition. 4. The maximum particle size of the metal oxide fine particles is 1,000.
The primer composition for a sealing material according to any one of claims 1 to 3, which has a thickness of not more than nm. 5. The primer for a sealing material according to claim 1, wherein the sulfonate-based surfactant is sodium alkylsulfonate, sodium alkylbenzenesulfonate, or sodium alkylnaphthalenesulfonate. -Composition. 6. The primer composition for a sealing material according to claim 1, wherein the resin is polyisocyanate. 7. The primer composition for a sealing material according to claim 1, wherein the sealing material is a polysulfide sealing material.