JPH02150488A - Primer composition and bonding operation - Google Patents

Abstract

PURPOSE:To improve weather resistance, heat resistance, toughness and adhesion with a hot melt adhesive by using a resin composition composed of a styrene- based thermoplastic block polymer, a rosin ester resin, a plasticizer, etc., as a primer. CONSTITUTION:A resin composition composed of (A) >=50wt.% (hydrolyzed) styrene-based thermoplastic block polymer (partially)modified by hydrolyzable active silyl groups and having 10000-50000 average molecular weight, (B) 50-10wt.% (silyl group-containing) (hydrogenated) rosin ester resin and/or (hydrogenated)petroleum resin-based tackifier and (C) 10-0wt.% plasticizer is diluted and dissolved so that the solid content may be 5-80wt.% to obtain the subject primer composition. Application of the above-mentioned composition to the joint surface of a glass lens part material of a car lighting, drying and baking are carried out in advance. The lighting is subsequently bonded thereto using a hot melt sealant or an adhesive seal.

Description

Detailed Description of the Invention [Industrial Field of Application of the Invention] The present invention provides a vehicle lamp lens material made of hard glass or soft glass (hereinafter referred to as glass), polyester resin (hereinafter referred to as PP), acrylonitrile- Primer composition and its adhesion used for adhesive sealing with housing material such as butadiene-styrene resin (hereinafter referred to as ABS), polyester resin (hereinafter referred to as BMC), gold RSM plate, pre-coated steel plate, etc. Regarding processing methods.

[Prior Art] Traditionally, hot-melt sealants based on various olefins have been used to adhesively seal the lens and housing parts of lamps for vehicles. Its usefulness is widely known, and it is gaining an increasingly important position from the standpoint of instant adhesiveness and non-pollution.

In recent years, vehicle lighting equipment has become more sophisticated, weighed, toughened, and larger, and instead of using hard glass as a material for lighting equipment, soft glass or semi-hard glass is frequently being used as a material for lighting equipment. It is starting to be used. For this reason, the current situation is that new hot melt sealing materials compatible with various glass materials are being actively developed.

Even under these circumstances, when glass lens materials are adhesively sealed, there is often a problem that the interfacial adhesion properties are impaired.

In other words, conventionally, when the above-mentioned glass materials were adhesive-sealed with a hot-melt sealant, the durability of the bond immediately after bonding was poor, and it was particularly resistant to erosion by various car wash chemicals. As a result, water leakage problems often occur due to 'AM' at the adhesive seal interface, and this type of problem often occurs especially in the production of lighting equipment in winter. For this reason, there has been a strong desire for a solution to this problem.

In addition, as a means to improve the adhesive durability of glass, a known method has been to apply a dilute solution of various low-molecular-weight silane coupling agents as a primer solution to the glass surface and then seal the glass surface with adhesive. However, as a result of study, this type of method has shown that the life after application is zero (
, it was found that there was a drastic change over time and that it was not reliable at all.

In other words, it has the weather resistance, chemical resistance, heat resistance, and other adhesive seal reliability required for vehicle lighting in various long-term environments, and even in winter, the initial chemical resistance is fully demonstrated. At present, there is a strong desire for a seal joining method, primers, and adhesive processing methods for this purpose.

To date, disclosure or adhesive processing of suitable sealing materials or primers that solve the above-mentioned initial adhesive durability when adhesive sealing of glass lens materials used as lens materials for vehicle lights has been performed. There is no disclosure of methods etc.

[Question B to be solved by the invention] Specifically, when adhesive bonding sealing is performed using a glass lens material, which is used as a lens material for vehicle lamps, there is a problem with the initial adhesive durability. Our goal is to provide an adhesive processing method that perfectly solves the problem and the primer adhesive composition necessary for that purpose.

[! Ili! Means for Solving II] As a result of intensive study on the above-mentioned problems, the present inventors found that the adhesive seal surface of the glass lens material for vehicles already has heat-resistant rigidity and toughness, and that the adhesive seal By applying a specified primer coating with strong adhesion and durability to the glass, which also has excellent adhesion with adhesives, and then joining the housing part with a hot-melt sealant or an adhesive sealant,
It has been found that the problem of initial adhesion durability can be completely solved, and the present invention has been achieved.

In other words, the present invention means that the average molecular weight is in the range of 10,000 to 500,000, and that at least 5% by weight is a resin modified with one or more hydrolyzable active silyl groups. 50% by weight or more of (hydrogenated) styrenic thermoplastic block polymer (a), (hydrogenated) rosin ester resin, or silyl group-containing (hydrogenated) rosin ester resin, and/or (hydrogenated) petroleum resin. Type tackifier (b) 5
A resin composition consisting of 0 to 10% by weight and 10 to 0% by weight of the stabilizer (c) is diluted and dissolved with a solvent to give a solid content of 5 to 80% by weight, and is made into a liquid at room temperature. A primer composition characterized by the above properties is applied in advance to the adhesive bonding interface of the glass lens material of a vehicle lamp, and then dried and baked, and then a hot-melt sealant or an adhesive sealant is applied to the lamp. This is an adhesive processing method for joining.

Preferably, the (hydrogenated) styrenic thermoplastic block copolymer (a) in which at least 5% by weight or more is a resin modified with at least one hydrolyzable active silyl group in the molecule is mainly Styrene-butadiene- as a chain
It is a hydrogenated product of a styrene block copolymer, and is preferably a completely hydrogenated product or a hydrogenated product with a weight average molecular weight in the range of 30,000 to 100,000, and particularly preferably,
At least 5% by weight or more of the resin is modified with at least one hydrolyzable active silyl group in the molecule,
(Hydrogenated) styrenic thermoplastic block copolymer (a)
is a hydrogenated product of a styrene-butadiene-styrene block copolymer or a hydrogenated product of a styrene-isoprene-styrene block copolymer as the main chain, and the styrene content in the block copolymer is 10% or more and 45% or less. It is preferable to use the above-mentioned primer composition within the range.

Preferably, the softening point temperature of the (hydrogenated) rosin ester resin, the silyl group-containing (hydrogenated) rosin ester resin, and/or the (hydrogenated) petroleum resin-based tackifier (b) is 85°C or higher. (hydrogenated) rosin ester resin and/or silyl group-containing (hydrogenated) rosin ester resin and/or (hydrogenated) petroleum resin-based tackifier (b) is rosin, polymerized rosin or Silyl group-containing rosin, rosin ester, or silyl group-containing rosin esters, C5 petroleum resin, dicyclopentadiene petroleum resin, terpene petroleum resin, or hydrogenated resins thereof, low molecular weight styrene resin, low molecular weight α - It is particularly preferable to use the primer composition using one or more types selected from methylstyrene resins and the like.

Furthermore, it is possible to use the primer composition in which the plasticizer (c) is one or more selected from naphthenic oil, paraffin oil, liquid polybutene, liquid hydrogenated polyisoprene, etc. There are no answer questions.

In addition, examples of solvents include ketones, alcohols, aromatic acid hydrocarbons whose boiling points range from room temperature to less than 200°C,
Il selected from trichlorethylene, trichloroethane, dichloroethane, cellosolve acetates, gasoline, kerosene, and aliphatic hydrocarbons! ! Alternatively, it is preferable to use two or more kinds of solvents, and the above-mentioned primer composition,
At the adhesive bonding interface of the glass lens material of vehicle lights,
It is highly preferable to use an adhesive processing method in which the primer composition of the present invention is applied in advance to a film thickness of 0.1 micron or more, dried, and then bonded using a hot melt sealant or an adhesive sealant. After coating and drying the adhesive interface of the glass lens material, hot-melt sealants based on butyl rubber, or styrene-ethylene-butylene-styrene block copolymer, or styrene-isoprene-styrene block copolymer, and The adhesive processing method using a reactive hot-melt adhesive is the most preferable because it not only provides reliability in the initial adhesive seal of the lamp but also has high productivity (and can be bonded in an extremely short time).

In the present invention, the primer composition of the present invention has the effect of exhibiting extremely remarkable adhesion durability, especially with glass, and the long-term performance life of the coating film is maintained with almost no change over time. An adhesive specified as the base polymer, wherein the chain is a (hydrogenated) styrenic thermoplastic block copolymer resin, and at least 5% by weight has at least one hydrolyzable active silyl group in the molecule. The composition is characterized by containing a imparting agent and, if necessary, a plasticizer.

The primer composition of the present invention is also a composition that has sufficiently good weather resistance, heat resistance, toughness, and adhesion properties with hot melt sealants or hot melt adhesives that are required for lamps, and is useful in the market. is very high.

In the present invention, the average molecular weight of the present invention is in the range of 10,000 to 500,000, and at least 5% by weight of the resin is modified with at least one or more hydrolyzable active silyl group in the molecule. (Hydrogenated) styrenic thermoplastic block polymer (a) refers to an active silyl group-containing styrene-butadiene-styrene block copolymer, or a hydrogenated product thereof, an active silyl group-containing styrene-isoprene-styrene block copolymer, or the same water. Additives, etc. are cited as examples of boat fishing; the former is referred to as active silyl group-containing SBS or 5EBS, and the latter is hereinafter referred to as active silyl group-containing 313 or 5EPS, and the following modification methods are adopted. can be obtained easily.

For example, commercially available products include Calyflex TR-1101 and TR-1102 manufactured by Shell Chemical Products, Turprene T-414 and Asaprene T-431 manufactured by Asahi Kasei Products, and
Styrene-butadiene-styrene block copolymer resin (hereinafter referred to as SBS resin) such as the trade name TR-2000 of Japan Synthetic Rubber Products, Kraton C; -1657, C-1652, G-16 of Shell Chemical Products.
50, G-1726X, G-1866, G-17
01, Mitsubishi Yuka products' trade names Labaron T-331 and 5J4400, and fat chemical products' trade name Tuftic H-1.
For example, a block copolymer resin represented by styrene-ethylene-butene-styrene bronze copolymer resin (hereinafter referred to as 5EBS resin) such as 041, 5EBS H-1051, and 5EBS H-1052 is treated with vinyl trimethoxy resin in a nitrogen stream. Silane, vinylsilanes such as vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, α-methacryloxymethyltrimethoxysilane, T-methacryloxypropyldimethoxymethylsilane, γ-methacryloxypropyltrimethoxysilane , acryloylsilanes such as γ-methacryloxypropyltriethoxysilane, (T-
Grafting is carried out by a known method using mercaptosilanes such as mercaptopropyl)methyldimethoxysilane, T-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc. in combination with a radical initiator, and at least A method for obtaining a resin modified so that 5% by weight or more, preferably 50% by weight or more, particularly preferably 80% by weight or more of a starting resin has active silyl groups in the molecule.

Alternatively, the SBS or 5EBS resin may be treated with an unsaturated acid such as (meth)acrylic acid or maleic acid using a known method.
Acids or anhydrides with double bonds such as maleic anhydride, and mercaptocarboxylic acid compounds such as mercaptopropionic acid are graft polymerized, that is, by a method in which an acid anhydride group or a carboxyl group is introduced in advance. resins (available as commercially available resins, such as Shell Chemical under the trade name Kraton FC-190).
1X, product name: Tuftic M-1913 as a fat chemical product
, M-1911, M-1943, M-1953, etc.), followed by, for example, γ-glycidoxypropyltrimethoxysilane, T-glycidoxypropylmethyldimethoxysilane, T-glycidoxypropylmethyldimethoxysilane, etc. By reacting with epoxysilanes such as xyprobyltriethoxysilane, T-glycidoxypropylmethyljethoxysilane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, at least 5% by weight of the starting resin % or more, preferably 50% or more, particularly preferably 80% or more by weight, a method for obtaining a resin modified so that it has active silyl groups in its molecules.

Also, for example, the above-mentioned SBS or 5EBS resin or styrene-
Isoprene-styrene block copolymer resins (hereinafter referred to as SIS), such as Shell Chemical products under the trade names Cariflex TR-1107, TR-1111, and T
R-1112, TR-1117, Nippon Gosei Kagaku product name 5IS5000, 5IS-X-6, 5IS-
X-7, EtJROPRENE SQL T-190 from EniChem Elastmeri, T=192, product name of fat chemical product Fintac 3420
, srs resin such as 3430, 3435, styrene-
ethylene-propylene IJII (hereinafter referred to as sEP),
For example, as a shell chemical product, the product name is Kraton G-17.
Using each of the SEP resins such as 01X, grafting treatment is performed using a known method such as hydroxy (meth)acrylic esters, hydrogen peroxide, or mercaptophenols to introduce a hydroxyl group as a functional group into the molecule. Further, by reacting with isocyanatosilanes such as T-isocyanatopropyltrimethoxysilane and T-isocyanatopropyltrimethoxysilane,
At least 5% by weight or more, preferably 50% by weight or more, particularly preferably 80% by weight or more of the starting resin is modified to have an active silyl group in the molecule, thereby easily obtaining a resin. .

In the present invention, the average molecular weight of the present invention is in the range of 10,000 to 500,000, and at least 5% by weight of the resin is modified with at least one or more hydrolyzable active silyl group in the molecule. , (hydrogenated) styrenic thermoplastic block polymer (a) has heat resistance when the average molecular weight is 10,000 or more,
Chemical resistance is impaired; on the other hand, if the average molecular weight is 500,000 or more, the viscosity of the primer solution tends to become extremely high, and the composition easily gels with moisture during handling.

(Hydrogenated) A resin modified with at least one hydrolyzable active silyl group in the molecule in a base polymer typified by a styrene thermoplastic block polymer.
Hydrogenated) styrenic thermoplastic block polymers cannot exhibit sufficient initial adhesion durability if the degree of modification is less than 511% by weight, and preferably 50% by weight or more.
Particularly preferably, it is used after being modified so that 80% by weight or more has an active silyl group in the molecule.

Further, in the present invention, the method for obtaining the (hydrogenated) styrenic thermoplastic block polymer (a) having active silyl groups may be prepared separately in advance by the method described above, or the tackifier according to the present invention may be used. There is no problem in carrying out the process in a system containing a plasticizer, a plasticizer, and a solvent at the same time.

In addition, the styrene content in the main chain polymer of the (hydrogenated) styrenic thermoplastic block polymer (a) having active silyl groups of the present invention is in the range of 5 to 45% by weight, preferably 12 to 20% by weight. The reason why it is desirable to use a block copolymer in the range of If the content is 45% or more, the primer coating will be hard and the low-temperature properties will be slightly lacking.

The tackifier (b) of the present invention is intended to improve adhesion and wetting properties to the glass surface of the adherend, and to improve adhesion with hot-melt sealants in the adhesive processing method of the present invention. It is an essential component for achieving this goal.

That is, the tackifier (b) of the present invention is a (hydrogenated) rosin ester resin, a silyl group-containing (hydrogenated) rosin ester resin, and/or a (hydrogenated) petroleum resin-based tackifier, The softening point temperature is preferably 85°C or higher in view of the heat-resistant adhesion properties of the primer coating, such as rosin, polymerized rosin, silyl group-containing rosin, rosin ester or silyl group-containing rosin ester, C5 petroleum resin, etc. Dicyclopentadiene petroleum resin, terpene petroleum resin,
Alternatively, these hydrogenated resins, low molecular weight styrene resins, low molecular weight α-methylstyrene resins, etc. are representative, and one or more types selected from these may be used.
1 m or 50 to 1 of two or more types per 100 of the resin composition
It is preferable to use it in the range of 0% by weight, preferably in the range of 20 to 10% by weight. If it is more than 50% by weight, the coating film will become abnormally hard and brittle, and if it is less than 10% by weight, it will become glassy or This is because the adhesion performance with the hot melt sealant becomes insufficient.

The plasticizer (c) of the present invention is the above-mentioned (hydrogenated)
Typical examples include naphthenic oil, paraffin oil, liquid polybutene, liquid hydrogenated polyisoprene, etc., which are compatible with the styrenic thermoplastic block copolymer and the tackifier. It is okay to use two or more of them. By including a plasticizer, it is possible to impart appropriate toughness to the primer coating, and it is suitable for systems with a high styrene content of the above-mentioned (hydrogenated) styrenic thermoplastic Pronk copolymer. It is very effective.

In the present invention, the solvent is used in order to make the primer composition liquid at room temperature, and to provide optimal workability and coating film thickness to the glass adherend surface with the necessary and sufficient primer coating thickness. The purpose of its use is to impart formability, and so that it becomes liquid at room temperature, the solid content is 5 to 80% by weight, preferably 5 to 50% by weight, particularly preferably 10 to 20% by weight.
It is best to dilute it with the following solvent to make a uniform solution.

In other words, the solvent of the present invention has a boiling point ranging from room temperature to 200°C.
For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, acetylacetone, acetophenone, alcohols such as cyclohexanol, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, acetoacetic acid Esters such as ethyl, ethers such as ethylene glycol motsubutyl ether, diethylene glycol monomethyl ether, furans such as tetrahydrofuran, methyl chloroform, dichloroethane, 1,1.
Halogen compounds such as 2-trichloroethane, 1゜2.3-trichloropropane, 1,1,2,2゜-tetrachloroethane, trichloroethylene, etc., aromatic hydrocarbons such as benzene, toluene, xylene, styrene, kerosene, mineral spirit, etc. Typical examples include aliphatic hydrocarbons such as n-hexane, n-octane, gasoline, and cyclohexane, and it is preferable to select and use one or more of these.

It is customary to select a solvent composition that is strong enough to prevent glass material from repelling, and a solvent composition that does not cause the active silyl group-containing lubricant of the present invention to react and deteriorate. Immediately after adjusting the composition, dry it,
In the adhesion pretreatment for forming the primer coating layer, it can be used without particular restrictions.

That is, the solvent of the present invention includes ketones, alcohols,
Typical examples are aromatic hydrocarbons, trichlorethylene, trichloroethane, dichloroethane, cellosolve acetates, gasoline, kerosene, and adipose hydrocarbons, and the use of a solvent selected from these or two or more solvents can achieve the desired purpose. achieved.

The reason why the boiling point of the solvent is in the range from room temperature to less than 200°C is because if a solvent with a boiling point of 200°C or higher is used, under -a paint film drying and baking conditions, the solvent may not be present in the paint film. This is because the solvent tends to remain and the chemical resistance tends to be poor, so it is particularly preferable to use a solvent with a boiling point in the range of 60°C to 150°C or less.

The liquid primer composition of the present invention may also contain various known additives, such as antioxidants, anti-aging agents, ultraviolet absorbers,
UV stabilizers, pigments, coloring agents, titanate coupling agents, hydrolysis accelerators typified by Van compounds such as diptyltin dilaurate, reaction accelerators typified by acetylacetone metal complex compounds, hydrolysis stimulators such as water, etc. PH of agents, inorganic acids, etc. 1! A conditioning agent, a surfactant such as a quaternary ammonium salt, etc. may be added and blended in advance or immediately before use.

In particular, in the liquid primer composition of the present invention, among the above-mentioned additives, a hindered phenol anti-aging agent is added in an amount of 1 part by weight or less per 100 parts by weight of the solid matter of the primer composition, and a hindered amine as an ultraviolet stabilizer is added. compound,
085 per 100 parts by weight of the solid matter of the primer composition
It is recommended to use a benzotriazole compound as an ultraviolet stabilizer in an amount of not more than 0.5 parts by weight per 100 parts by weight of the solid matter of the primer composition because it has a high effect of improving weather resistance. preferable.

Particularly preferably, a hydrolysis accelerator (catalyst) typified by dibutyltin laurate among the above-mentioned additives is added to the liquid primer composition of the present invention based on 100 parts by weight of the solid matter of the primer composition. It is particularly preferable to add 0.2 parts by weight or less to the primer composition of the present invention immediately before use, since good adhesive properties can be exhibited during primer baking at low temperatures.

Methods for applying the liquid primer composition of the present invention include, but are not limited to, brush coating, spray coating,
There are bar coater coating, applicator coating, etc., and any method that can apply a thin layer to the joint surface of the glass lens material of the vehicle lamp is fine. Usually, the thickness is 0.5 to 150 microns, preferably 2 to 100 microns. It is preferable to have a thickness of 10 microns.

The method of drying and baking after applying the liquid primer composition of the present invention is preferably a method such as far infrared heating, hot air drying, vacuum heating drying, etc., and is usually 50°C to 150°C, preferably 80°C to 120°C. Heat and dry in the temperature range of C,
By drying for about 30 minutes to 30 degrees, a coating film with high initial adhesion durability is formed.

After forming a primer coating film on the joint portion of the glass lens material of a vehicle lamp using the liquid primer composition of the present invention, a conventional hot melt sealing material for headlamps, such as JP-A-60 -92379, 6
2-129373, 62-227981, 62-2
Butyl rubber-based hot melt adhesives, partially cross-sulfurized chlorinated butyl rubber-based hot melt adhesives, hydrogenated styrene block polymer-based sealants and reactive hot melt adhesives disclosed in US Pat. Adhesive for epoxy seals mixed with base ingredients, UV-curable epoxy seal adhesives, moisture-curable urethane seal adhesives, urethane seal adhesives with two-component mixtures, foam-type urethane seals Thermosetting sealing adhesives such as acrylic sealing adhesives, acrylic sealing adhesives, silicone sealing adhesives, etc. may be used, and they have the weather resistance and heat resistance necessary for lamp adhesives. ,
In addition, an adhesive processing method can be adopted in which adhesive bonding is performed using a hot melt type sealing material or an adhesive called a hot melt adhesive and a thermosetting adhesive sealing agent that are rich in adhesive and durable sealing properties.

Particularly preferably, it has a melt viscosity of 170°C to 190°C, a range of 30,000 to 100,000, an open time of 2 to 3 minutes, no fluidity at 80°C to 90°C, and a base Examples of polymer components include butyl rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, or hydrogenated products thereof, ethylene-ethyl acrylate resin, ethylene-vinyl acetate resin, acrylic resin, polyisoprene. A hot-melt sealant made of one or more base polymers selected from resins, polyisobutylene resins, ionomer resins, etc. exhibits good adhesion to the resin coating of the primer composition of the present invention. This can be cited as a preferable example.

That is, the adhesive processing method of the present invention is to apply the primer composition solution of the present invention to the bonding surfaces of the glass lens parts of lamps, etc., which are to be bonded in advance, and apply and dry bake them. Later, the housing member and
This is an adhesive processing method that completely seals the parts using an adhesive sealant such as the hot-melt sealant described above.

(Examples) Examples of the present invention will be described below, but the expressions "%" and "%" in the examples mean parts by weight and % by weight, and the examples do not particularly limit the present invention.

In addition, the initial adhesion reliability test described in the examples was conducted using the following test method.

The thickness of the hard glass and soft glass is 3mm.

Prepare a 2.5 cm x 10 cm glass plate, apply the primer composition described in the example on one side using a bar coater, and immediately dry in a hot air dryer at 80 to 120"C.
A dry baking treatment was performed for 10 to 20 minutes to obtain treated test pieces each having a film thickness of 1 to 5 microns.

On the other hand, separately prepared polypropylene resin (hereinafter abbreviated as PP) or ABS with a thickness of 3 mm and a size of 2.5 cm x 10
The hot-melt sealant described in the examples was applied to the flat surface of a 5 cm flat plate using a hand gun at an application temperature of 190°C in a bead shape of 5 to 10 mm in width and 5 cm in length, and immediately the primer-treated test piece was applied. , and an untreated glass test piece were bonded to the primer-coated surface and the untreated surface, respectively, and left at room temperature for 1 hour. Then, a 3 mm thick wedge and a small amount of gauze were inserted into the gap between the bonded end surfaces. Gauze was impregnated with the various chemicals described in the examples and left to stand for a maximum of 3 days, and it was observed whether the glass interface peeled off.

Example 1 Using a kneader-ruder device with a capacity of 110 liters, 1
At 50°C to 180°C, butyl rubber product name Butyl 06
5 (Nippon Butyl Products) 900 parts and styrene-ethylene graft-modified with 2% vinyltriethoxysilane
800 parts of butylene-styrene block copolymer and hydrogenated petroleum resin trade name Clearon P-12 as a tackifier.
5 (cheap crude oil product) 1300 copies, also Escolesh 5
320 (Tonex Co., Ltd. product) 700 parts, polypropylene wax trade name Viscole 66 as a wax component
0P (Sanyo Chemical Products) 200 parts, liquid polybutene as plasticizer trade name HV-300 (Japan Petrochemical Products) 35
0 parts, titanium oxide 50 parts, carbon black 0.5 parts,
Atatsuchi” Tsuku Polypropylene (hereinafter referred to as APP) (
Mitsui Toatsu Chemical Co., Ltd. product) 500 copies and screws (2, 2, 6, 6-
25 parts of tetramethyl-4-piperidyl) sebacate, pentaerythrityl-tetrakis (3-(3,5-di-t)
-butyl-4-hydroxyphenyl)propionate 3
50 parts, 2-(2-hydroxy-3゜5-bis (α,
After uniformly melting and kneading 25 parts of α-dimethylbenzyl)phenyl]benzotriazole and completely defoaming, a gray hot-melt sealing material (1) was obtained.

The melt viscosity of this product at 190° C. was 98,000 centipoise (B-type viscometer).

Furthermore, there was almost no fluidity at 90°C, and the softening point was 136°C (ring and ball method).

Example 2 Using a 1-liter capacity Ni-Goo-Roo-Goo device, 14
Styrene-isoprene-styrene block copolymer trade name Califlex TR-1107 (at 0°C to 170°C)
Shell Chemical Products) 750 parts, same as Cariflex T
500 parts of R-1112 (Shell Chemical Products), 1500 parts of hydrogenated petroleum resin trade name Alcon P-125 (Rough Chemical Products) as a tackifier, and 600 parts of Meiko Scollett 5320 (Tonex product), also the same product. Product name: YS Polyster T-130 (cheap crude oil product) 250
and as a wax component, the product name is Viscole 660P.
(Sanyo Kasei product) 250 parts and product name Hiwax 60
100 parts of 0P (Mitsui Petrochemical Products), 350 parts of naphthenic oil (trade name: Flex #205ON (Fuji Kosan Products) as a plasticizer, 2 parts of carbon black, and octadecyl-3-(3,5-G) as an antioxidant. Butyl-
After uniformly melting and kneading 50 parts of 4-hydroxyphenyl) propionate, 20 parts of tris(2,4-di-butylphenyl) phosphite, and 628 parts of APPSL grade (Mitsui Toatsu product), and completely defoaming. A black hot-melt sealant (2) was obtained.

Example 3 Using a 4 flask reactor with a capacity of 1 liter, Shell Chemical Products, trade name KRATON FG-1901X was used.
(2% maleic anhydride graft modified 5EBS resin) 200g, toluene 200g, r-glycidoxypropyltrimethoxysilane 5g, triethylamine 0. Charge Igr and perform a grafting reaction at 120°C under nitrogen for 20 hours to obtain a resin whose weight is at least 50% modified with hydrolyzable active silyl groups (unmodified resin is 50% by weight or less). A solution of silyl-modified 5EBS-1 with approximately 50% solids was obtained.

Example 4 Using a 4-ton flask reactor with a capacity of 1 liter, 200 gr of Asahi Kasei's Toughtic M-1913, 460 gr of xylene, and 10 gr of β-(3°4 epoxycyclohexyl)ethyltrimethoxysilane were prepared. , triethylamine O, 1gr, and heated at 140°C under nitrogen for 15 minutes.
at least 70% by weight by carrying out the grafting reaction for a time
A solution of silyl-modified 5EBS-2 of about 30% solids was obtained, which was a resin modified with hydrolyzable active silyl groups (less than 30% by weight of unmodified resin).

Example 5 Using a 4-bottle flask reactor with a capacity of 1 liter, 200 gr of Asahi Kasei's Toughtic M-1943, 400 gr of toluene, and 200 g of cyclohexanone were added.
3.0 gr of r, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, and 0.2 gr of ris dimethylaminobenzylphenol were heated at 110°C under nitrogen.
, the grafting reaction was carried out for 15 hours, and the grafting reaction was carried out for 15 hours.
Solid compound 25 whose weight percent or more is resin modified with hydrolyzable active silyl groups (unmodified resin is 70 weight percent or less)
A solution of 5% silyl-modified 5EBS-3 was obtained.

Example 6 Using a closed kneader with a capacity of 1 liter, 400 gr of Shell Chemical Products, trade name KRATON G-1657 (SRBS resin) and 55 g of vinyltriethoxysilane were added.
gr, and under nitrogen at 150°C, 1.0 part of benzoyl peroxide was divided into 5 parts, added every hour to each part, and the grafting reaction was carried out at the same temperature to obtain at least 20% by weight.
The above is a resin modified with a hydrolyzable active silyl group (unmodified resin is 801% or less), and a toluene solvent is added.
Silyl-modified SEBS-478 with approximately 50% solids
I got some liquid.

Example 7 Using a 4 flask reactor with a capacity of 1 liter, a chemical reaction product manufactured by Shell Chemical Products, trade name Cariflex TR-1101 (trade name) was prepared.
150 gr of SBS resin), TR-1107 (SIS
50g of resin), 200g of toluene, and 7.5g of vinyltrimethoxysilane or 3gr of T-mercaptopropyltrimethoxysilane were added and heated under nitrogen for 1 hour.
20℃.

Peroxide 1.1-bis(-butylperoxy) 3°3.5
- 1.0 part of trimethylcyclohexene is divided into 5 parts, added every 2 hours to each part, and a grafting reaction is carried out at the same temperature, so that at least 10% by weight of the resin is modified with hydrolyzable active silyl groups (unused). Silyl-modified SBS/5IS-1 with approximately 50% solids content (901% or less)
I got a solution.

Example 7 Using a 4 flask reactor with a capacity of 1 liter, a 4 flask reactor with a capacity of 1 liter was used.
50 gr of SBS resin), 150 gr of a synthetic resin product, trade name Fintac 3430 (313 resin), 220 gr of toluene and 10 gr of mercaptophenol, heated at 120°C under nitrogen, and divided 1.0 part of benzoyl peroxide into 5 parts. After the grafting reaction was carried out at the same temperature, 10 parts of T-isocyanatopropyltrimethoxysilane was added every 30 minutes, and at least 25% by weight of T-isocyanatopropyltrimethoxysilane was composed of hydrolyzable active silyl groups. A silyl-modified SBS/SI S-2 solution of approximately 50% solids with modified resin (less than 75 parts % unmodified resin) was obtained.

The dry film thickness is approximately 1.5 on glass and soft glass plates, respectively.
Apply to a thickness of ~2 microns and dry with a hot air dryer for 11
It was dried at 0°C for 10 minutes and used as a test piece.

Examples A-D (Examples of the present invention) Liquid primer compositions were prepared at the blending ratios shown in Examples A-H in Tables 1 and 2, and hard Table-1: Primers A to D Examples ! -L (Comparative Example) A comparative liquid primer composition was prepared at the blending ratios shown in Examples G to J listed in Table 3, and a dry film thickness of approximately Coat to a thickness of 1.5 to 2 microns and dry in a hot air dryer at 10°C/10
The sample was dried for 30 minutes and used as a comparative test piece.

Table-2 Primers E to H Table-3 = Comparative Primer r -L Example M (Comparative Example) Polytetramethylene glycol monomethyl ether with molecule I2000. 1st addition of 2.1 mol of isophorone diisocyanate and hydroxyethyl methacrylate to 0.3 mol of polyol obtained by addition polymerization of 4 mol of propylene oxide to 7 mol of bisphenol A and 1 mol of bisphenol A. 97.5 parts of urethane acrylate resin and 2.5 parts of T-methacryloxypropyltrimethoxysilane, which were obtained by reacting the same, were added with the product name Irgacure #651 (product of Ciba Geigy) 2 as an ultraviolet polymerization initiator. , a UV-curable liquid primer composition (Primer M) was obtained.

In the case of a primer, the coating film was irradiated with UV using an 80W Lan 14 wood UV irradiation device, and a 2-3 micron hardened primer coating was formed on the adherend (soft glass plate) and used for comparison tests. did.

The adhesion of the coating film itself using each of the primer compositions obtained in Examples A to M, and the initial adhesion durability after bonding using the hot melt adhesive described in Examples 1 to 2. The results of the sex test are shown in Table 4.

The above results were the same for the adhesive bonded test pieces prepared in Examples A-M immediately after the primer coating was formed and after being left in a clean room for two weeks. The results were shown.

Examples N-Q (Comparative Example) A 2% ethyl acetate solution of T-glycidoxyprobyltrimethoxysilane was prepared and used as a Primer N solution. Also, 3 of T-methacryloxypropylitriethoxysilane
% toluene solution was prepared and used as a primer 〇 solution. In addition, a 2% xylene solution of vinyltriethoxysilane was prepared and used as a primer P solution.

Further, a 1% ethyl acetate solution of T-aminopropyltrimethoxysilane was prepared and used as a Primer N solution.

Primer N-R was applied to a hard glass plate by dipping and baked in a hot air dryer at 80°C to 120°C for 10 minutes. A test piece obtained was tested for the initial adhesion durability described above. Tested.

Immediately after the primer coating is formed and after the coating is formed, release it into a clean room! Table 5 shows the results of the initial adhesion durability test (using a 50% aqueous solution of Uncoater A) using the hot melt sealant prepared in Example 1 after two weeks.

Table 5 Primer initial adhesion durability test; ◎ No interface '7.1lril at all.

On the 03rd, very slight wrinkles were observed (59a, 7 interfaces, 21 years ago, J Yu Δ209A-, 50% city O, Wei chin retention, 1 part).

× 50% Tsu Jyu 1 ka b Mataban Kashi Tokokai ■ Ho 1 intestine was observed.

From the results of Examples N-Q, the initial adhesion durability test regarding detergent resistance showed that the paint film was relatively usable immediately after it was formed, but the paint film underwent severe oral changes and was completely impractical. .

In addition, in the adhesive bonding method using the primer of Examples N-Q, it is estimated that the chemical bond between the primer coating film and the adhesive sealant cannot be expected to be strong, and the reliability of the adhesive bonding under long-term stress is poor. In particular, the test results for long-term water resistance (after 30 days of immersion in 40°C hot water) and weather resistance (after 1 year of outdoor use) showed that peeling occurred near the glass interface and was poor. In similar tests using the primers of Examples A-)f as described, no abnormal phenomena were observed.

Furthermore, using the primer compositions of Examples A and B described as examples of the present invention and the gray hot-melt sealant obtained in Example 1, a primer-treated hard glass material and a PP material were bonded. In this case, the tensile shear strength is 19-23 kg/c before the heating test.
ab” / 20℃, 80℃ heating / 30 days later 16.5
-22 kg/am"/20°C, and 19-23 kg/am"/20°C after 30 days of immersion in 40°C warm water.
16.0-21 kg/cm" after 24 hours of immersion in a 10% aqueous solution of Uncoater-A immediately after adhesion at 720°C, 15.
0-19 kg/cm''/20''C, it was confirmed that there were no problems, and the adhesive sealing material was peeled off as expected.

On the other hand, obtained in Example 1 when no primer was applied,
When a hard glass material and a PP material are bonded using a gray hot-melt sealant, the normal tensile shear strength immediately after bonding is 21 kg/cm at 20"C, respectively.
”, 80°C heating/30 days later 16 21 kg/c
s', Immediately after adhesion, uncoater resistance after 24-hour immersion in AlO% aqueous solution 2-3 kg/cs + "720" C1 Immediately after adhesion, resistance 5T-7 after 24-hour immersion in 10% suspension aqueous solution 1. 0 1. 5 kg/cm''/20°C, and especially in the detergent resistance test immediately after adhesion, the strength was greatly reduced due to interfacial destruction, which was a problem.

From this, it can be said that the coating film of the primer composition of the present invention has excellent initial adhesion durability to glass lens material and adhesion to hot melt sealants.

From the above results, it is clear that in the present invention, when bonding the glass lens part of the vehicle lamp and the 71 housing, the water leakage problem caused by the above-mentioned problem of initial bond durability and reliability does not occur at all. It has been shown that adhesive processing is possible without any problems.

In addition, the manufacturers for the codes listed in the table in the example are as follows.

5EBS (styrene-ethylene-butylene-styrene block copolymer) Kraton G-1652, Kraton G-1657; Shell Chemical SIS (styrene-isoprene-styrene block copolymer) Kaliflex TR 1107? Shell Chemical SBS (styrene-butadiene-styrene block copolymer) Asabrene T-431; Asahi Kasei Realon P-125 (hydrogenated petroleum resin); Cheap crude oil Escorez 5300 (hydrogenated petroleum resin); Tornex Alcon I'-125 (water Added petroleum resin); Arayo Chemical Super Ester A-115 (rosin ester resin)
;Arayo Chemical Ristarenox #3100 (α-methylstyrene 41
J11); Rika Vercules HV-300
(liquid polybutene); Nippon Petrochemical 5T-7 (solvent for cleaning vehicle parts such as automobiles); Yushiro Chemical Uncoater A (cleaning liquid); Yushiro Chemical window washer fluid (liquid specified by car manufacturer); Alcohol and surfactant [Effects of the Invention] According to the adhesive processing method using the primer composition of the present invention, it is difficult to assemble lamps etc. due to poor initial adhesive durability in the conventional adhesive processing methods. This will solve the problem of water leakage, which often occurs in large numbers, especially in the winter.

Furthermore, the present invention eliminates the problems associated with the product life of the paint film that occur with the primer treatment method that uses a silane coupling agent alone, which is conventionally known for boat fishing.

In other words, stable effects can be expressed.

Furthermore, according to the adhesive processing method using the primer composition of the present invention, a hot melt sealing material or a hot melt adhesive based on a known butyl rubber elastomer having excellent weather resistance, heat aging resistance, toughness, and heat resistance can be used. The lamp sealing properties can be used without any performance problems, and the lamp sealing properties can be fully demonstrated not only initially but also over a long period of time, and the sealing performance of vehicle lamps can be greatly improved.

Furthermore, the present invention can be widely applied not only to the sealing of glass lamps for vehicles, but also to the field of adhesive fixing and sealing of glass plates for building materials and ships, and is widely used in the field of adhesive processing related to adhesive bonding of glass materials and different materials. It is something that can be implemented.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A resin with an average molecular weight in the range of 10,000 to 500,000, and at least 5% by weight of the resin modified with at least one hydrolyzable active silyl group in the molecule. , 50% by weight or more of (hydrogenated) styrenic thermoplastic block polymer (a), (hydrogenated) rosin ester resin, or silyl group-containing (hydrogenated) rosin ester resin, and/or (hydrogenated) petroleum resin. A resin composition consisting of 50 to 10% by weight of the tackifier (b) and 10 to 0% by weight of the plasticizer (c) is diluted with a solvent to a solid content of 5 to 80% by weight. Using a primer composition that dissolves and becomes liquid at room temperature, it is applied in advance to the adhesive bonding interface of the glass lens material of a vehicle lamp, and then dried and baked.
A primer composition and an adhesive processing method thereof, characterized in that they are used to bond lamps using a hot-melt sealant or an adhesive sealant. 2. At least 5% by weight or more contains at least 1 in the molecule
A (hydrogenated) styrenic thermoplastic block polymer (a
) is a hydrogenated product of styrene-butadiene-styrene block copolymer as the main chain, and is a fully hydrogenated product with a weight average molecular weight in the range of 30,000 to 100,000, or a hydrogenated product of 85% or more. A primer composition and an adhesion processing method thereof according to claim 1, characterized in that: 3. At least 5% by weight or more contains at least 1 in the molecule
(Hydrogenated) styrenic thermoplastic block copolymer (hydrogenated) resin modified with hydrolyzable active silyl groups
a) is either a hydrogenated product of a styrene-butadiene-styrene block copolymer or a hydrogenated product of a styrene-isoprene-styrene block copolymer as the main chain, and the styrene content in the block copolymer is 10
% or more and 45% or less, the primer composition and adhesive processing method thereof according to claim 2. 4. (Hydrogenated) rosin ester resin or silyl group-containing (
The primer composition according to claim 1, wherein the softening point temperature of the tackifier (b) based on a (hydrogenated) rosin ester resin or a (hydrogenated) petroleum resin is 85°C or higher. and its adhesive processing method. 5. (hydrogenated) rosin ester resin or silyl group-containing (
Hydrogenated) rosin ester resin and/or (hydrogenated) petroleum resin-based tackifier (b) is rosin, polymerized rosin, silyl-modified polymerized rosin, rosin ester or silyl-modified rosin esters, C5 petroleum resin, It is characterized by using one or more types selected from cyclopentadiene petroleum resins, terpene petroleum resins, hydrogenated resins thereof, low molecular weight styrene resins, low molecular weight α-methylstyrene resins, etc. A primer composition and an adhesion processing method thereof according to claims 1 to 3. 6. Claim 1, wherein the plasticizer (c) is one or more selected from naphthenic oil, paraffin oil, liquid polybutene, liquid hydrogenated polyisoprene, etc. The primer composition and its adhesion processing method described in Section 1. 7. Ketones, alcohols, aromatic hydrocarbons, trichloroethylene, trichloroethane, dichloroethane, with boiling points ranging from room temperature to less than 200°C as solvents;
The primer composition and its adhesion according to claim 1, characterized in that one or more solvents selected from cellosolve acetates, gasoline, kerosene, and aliphatic hydrocarbons are used. Processing method. 8. Apply and dry the primer composition according to claims 1 to 7 on the adhesive bonding interface of the glass lens material of the vehicle lamp to a film thickness of 0.1 micron or more. An adhesive processing method characterized by bonding using a hot-melt sealant or an adhesive sealant. 9. The primer composition according to claim 1,
Coat the adhesive interface of the glass lens material of the vehicle lamp in advance to a film thickness of 0.1 micron or more, and after drying, apply butyl rubber-based and/or styrene-ethylene-butylene-styrene block copolymer-based and/or styrene. - An adhesive processing method characterized by bonding using an isoprene-styrene block copolymer-based hot-melt sealant or a reactive hot-melt adhesive thereof. 10. The primer composition according to claim 1 is coated on the adhesive interface of the glass lens material of a vehicle lamp to a film thickness of 0.1 micron or more and dried, and then an epoxy resin-based An adhesive processing method characterized by bonding using an adhesive sealant or a reactive adhesive sealant such as a urethane adhesive sealant, an acrylic adhesive sealant, or a silicone adhesive sealant.