JPH1135643A - Polymerizable composition, adhesive therefrom and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable composition capable of being directly coated on the surface of a molding product and adhering thereto even by a short time light radiation without surface treatment of a plastic, especially even without a primer treatment to a polyolefin molding product, and further to obtain a laminate of the polyolefin, etc., having strong adhesive power even at a high temperature by using the composition. SOLUTION: This polymerizable composition comprises a chlorinated polyolefin, a metal salt, a radical initiator, a compound having one or more polymerizable functional groups, water and/or an alcohol, and optionally an organic ionic coloring agent. The adhesive comprises the composition. The olefin laminate is formed by directly coating the adhesive on a polyolefin molding product without a primer, and irradiating light in a region from visual light to infrared rays.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable composition, and more particularly, to a polymerizable composition which can be used for adhesives, fillers, paints, inks and the like. In particular, the polymerizable composition of the present invention can be applied directly onto a polyolefin molded article without using a primer to bond the polyolefin molded article. This polyolefin laminate has strong adhesive strength even at high temperatures.

[0002]

2. Description of the Related Art Polyolefin resins are high in production, inexpensive, have a high degree of freedom in design, and have many excellent properties such as light weight, rust prevention, chemical resistance, water resistance, impact resistance, and good electrical properties. It is a general-purpose resin that has properties and is widely used in the fields of automobiles, home electric appliances, containers, packaging, and miscellaneous goods. Especially in the automotive field,
In response to needs such as weight reduction and luxury, for example, conversion from polyurethane bumper to polypropylene bumper,
The use of foamed polypropylene as a shock absorber and the conversion of ABS (acrylonitrile-butadiene-styrene copolymer) resin for interior components such as door trims and instrument panels to polypropylene resin are progressing. Polypropylene has been widely used for washing tubs for washing machines, tray members for refrigerators, television back covers, speaker housings, cooler housings, computer housings, and the like. However, polyolefin resin has a higher crystallization rate than other plastics (polyurethane resin, polyamide resin, acrylic resin, polyester resin, etc.) and is non-polar, so it is difficult to bond, paint and print. Had disadvantages.

Conventionally, when bonding, painting and printing a polyolefin molded product, the surface of the molded product is usually subjected to corona discharge, plasma treatment, gas flame treatment, chemical treatment or the like to activate the molded product surface, Is applied and heated and dried to activate the surface of the molded body, and then the surface of the activated molded body is bonded, coated, and printed. Further, as a special adhesive which does not require a primer, an adhesive prepared by mixing a chlorinated polypropylene solution and an acrylic emulsion with a tackifier resin has been proposed (Japanese Patent Laid-Open No. Hei 4-320474). This adhesive is heated to about 100 ° C. in use. Others Two-component compositions containing a chlorinated polyolefin as a main component have been proposed. These compositions are of a two-part type using a modified chlorinated polyolefin obtained by graft-polymerizing a hydroxyl group-containing acrylate or a hydroxyl group-containing methacrylate or a mixture thereof onto a chlorinated polyolefin and an isocyanate as a curing agent (Japanese Patent Laid-Open No. 58-171
74, JP-A-58-194959, JP-A-62-953
72, Tokuhei 2-36617).

[0004]

In the above-mentioned ordinary methods of adhesion, coating and printing, physical and chemical treatments such as corona discharge, plasma treatment, gas flame treatment and chemical treatment are performed in advance to improve the surface of polyolefin resin. There are problems such as the necessity of a target surface treatment, the application of a primer and the drying by heating, the increase in the number of steps, and the time required for completing the polymerization. The adhesive of the above-mentioned patent without a primer (JP-A-4-320474) also had to be heated after application. In addition, the two-pack type has drawbacks such as the necessity of adjusting the composition and the curing agent before use, the necessity of cleaning the line after use, and the wasting of the remaining adjustments. there were. Furthermore, in the field of automobiles and household electric appliances, a strong adhesive force at a high temperature after bonding a polyolefin molded article is required. The present invention has been made in order to solve the above-described problems, and has an object to provide a molded article such as a corona discharge, a plasma treatment, a gas flame treatment, a chemical treatment, and other physical and chemical treatments, and a primer treatment. An object of the present invention is to provide a polymerizable composition capable of directly applying an adhesive, a paint, or an ink to the surface of a molded article without the surface treatment step.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies and as a result, a specific polymerizable composition can directly adhere to a polyolefin molded body which has been difficult to directly adhere. And completed the present invention. The present invention includes the following items. A polymerizable composition comprising a chlorinated polyolefin, a metal salt, a radical initiator, a compound having one or more polymerizable functional groups, and water and / or an alcohol. A polymerizable composition comprising a chlorinated polyolefin, a metal salt, a radical initiator, a compound having at least one polymerizable functional group, an organic ionic dye compound, and water and / or an alcohol. The polymerizable composition according to the above item or the item, wherein the chlorinated polyolefin is modified. 4. The polymerizable composition according to any one of the above items 1 to 3, wherein the acid value is a chlorinated polyolefin having an acid value of 2 mgKOH / g or more. An adhesive comprising the polymerizable composition of any one of the above items. A laminate in which at least one of the molded articles to be bonded is a polyolefin, polyvinyl chloride, or ABS, and the molded article is adhered using the adhesive described in the above item.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The polymerizable composition of the present invention is a composition containing a chlorinated polyolefin and a compound having at least one polymerizable functional group. It is characterized by including salt, water and / or alcohol. The polymerizable composition of the present invention has no physical treatment such as corona discharge, plasma treatment, gas flame treatment and chemical treatment, pretreatment such as primer treatment, not only thermal polymerization, but also visible light. Or, since it can be polymerized by light in the near infrared region, for example, even in the case of a polyolefin molded article containing an ultraviolet absorber, it can be easily and effectively adhered and coated without being hindered by these ultraviolet absorbers and pigments. There is an advantage that printing can be performed. A polyolefin laminate formed by bonding a polyolefin molded article using the composition of the present invention has a strong adhesive force even at high temperatures. Here, as the polyolefin laminate,
Examples include automotive parts such as instrument panels, console boxes, rear seat backs, and door trim panels. Here, polypropylene is taken as an example of the polyolefin molded body, but is not limited thereto.

Hereinafter, the components constituting the present composition will be described in detail. The chlorinated polyolefin that can be used in the composition of the present invention imparts adhesiveness, adhesion, and the like to the composition, and basically has a normal chlorination rate of 1.5 to 1.5.
A chlorinated polyolefin of 50% by weight can be used, but a chlorinated polyoleofin modified with a carboxylic acid, a polyol (for example, a (meth) acrylate having a hydroxy group) or the like is desirable for enhancing the adhesiveness. Further, those having a functional group which acts as an acid and ion-crosslinks with a metal salt, particularly carboxylic acid-modified chlorinated polyolefin, are more preferable. This carboxylic acid-modified chlorinated polyolefin has an acid value of 2 mgKOH / g (resin).
The above is particularly effective in increasing the adhesiveness. Examples of commercially available carboxylic acid-modified chlorinated polyolefins include those having the following trade names. Supercron S-699, Supercron 844LM, Supercron 822, Supercron 892L, Hardlen 13
-MLJ, Hard Wren 14-MLJ, Hard Wren B-1
3MLJ, Hardlen CY-9020A, Hardlen C
Y-9122T, Hardlen CY-9122P. In the above, Supercron is manufactured by Nippon Paper Industries, and Hardren is manufactured by Toyo Kasei Kogyo.

The metal salt that can be used in the present composition is
Any metal salt can be used as long as it forms ionic crosslinks with the chlorinated polyolefin. Examples of metal salts include: Lithium hydroxide, lithium oxide,
Sodium hydroxide, beryllium oxide, magnesium oxide, calcium oxide, zinc oxide, lead oxide, cadmium oxide. These can be used alone or in combination of two or more.

The radical initiator that can be used in the composition of the present invention is basically any one that generates a radical by heat or light. Such radical initiators include organic azobis compounds, organic peroxides, organic boron compounds, and the like. These can be used alone or in combination of two or more. Examples of the organic azobis compound that can be preferably used in the present invention include 2-cyano-2-propylazoformamide, 1,1′-azobis (cyclohexane-1-carbonitrile), and 2,2′-azobis (2 -Methylbutyronitrile), 2,2′-azobisisobutyronitrile,
2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), Dimethyl 2,2′-azobisisobutyrate,
2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N
-[1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis [2-methyl-N -(2-hydroxyethyl) propionamide, 2,2'-azobis [2- (hydroxymethyl) propionitrile], and the like.

Examples of the organic peroxide which can be suitably used in the present invention include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane,
1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) cyclododecane, 2,2-bis (tert-butylperoxy) butane, normal butyl-4,4-bis (tert-butyl) L-butylperoxin) valerate, 2,2-bis (4,4-ditert-butylcyclohexyl) propane, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, Tertiary butyl hydroperoxide, α, α'-bis (tertiary butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-
2,5-bis (tert-butylperoxy) hexene, tert-butylcumyl peroxide, di-tert-butylperoxide, 2,5-dimethyl-
2,5-bis (tert-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, Bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, cumylperoxyneodecanoate, tert-butylperoxypivalate, tert-butylperoxybenzoate, bis (tersha L-butylperoxy) isophthalate, 3,3 ', 4,4'
-Tetra (tert-butylperoxycarbonyl)
Benzophenone and the like can be mentioned.

The organic boron compound that can be suitably used in the present invention is represented by the following general formula (1). General formula (1): [Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group,
An alkynyl group, an alicyclic group, a heterocyclic group, or an allyl group, each of which may be the same or different, and two or more of which may form a cyclic structure by bonding Often, Z ⁺ is an alkali metal ion, an alkaline earth metal ion or a general formula (2): (Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, an alkyl group,
A group selected from an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, and an allyl group, which may be the same or different; Or more may combine to form a cyclic structure).

Examples of the organic boron compound of the general formula (1) include tetramethylammonium n-butyltrianisylboron, tetramethylammonium n-butyltriphenylboron, tetramethylammonium n-octyltrianisylboron, tetramethylammonium n-octyltriphenylboron, tetramethylammonium n-butyltolylboron, tetramethylammonium n-butyltriphenylsilylboron,
Tetraethylammonium n-butyltrianisyl boron, tetraethylammonium n-butyltriphenylboron, tetraethylammonium n-octyltrianisylboron, tetraethylammonium n-
Octyl triphenyl boron, tetraethyl ammonium n-butyl triphenylsilyl boron, tetraethyl ammonium n-butyl tritolyl boron, tetraethyl ammonium tetra n-butyl boron, trimethyl ammonium hydrogen n-butyl trianisyl boron, trimethyl ammonium n-butyl triphenyl Boron, ammonium trimethyl hydrogen n-butyltrianisyl boron, ammonium trimethyl hydrogen n
-Butyltriphenylboron, ammonium tetrahydrogen n-butyltrianisylboron, tetrahydrogenammonium n-butyltriphenylboron, tetrahydrogenammonium tetraphenylboron, tetran-butylammonium n-butyltrianisylboron, tetran
-Butyl ammonium n-butyl triphenyl boron, tetra n-butyl ammonium n-butyl tritolyl boron, tetra n-butyl ammonium n-butyl triphenylsilyl boron, sodium n-butyl triphenyl boron, sodium n-butyl tritolyl boron , Sodium tetraphenylboron, potassium n-butyltriphenylboron, potassium n-butyltolylboron, potassium tetraphenylboron and the like.

As the compound having one or more polymerizable functional groups that can be used in the present invention, basically any compound can be used as long as it can be radically polymerized by the above-mentioned radical initiator. And a compound having an ethylenically unsaturated bond is preferable, and a compound having at least one acryloyl group or methacryloyl group in the molecule is particularly preferable. Examples of the compound having at least one acryloyl group or methacryloyl group in a molecule that can be suitably used in the present invention include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and isoamyl acrylate. , Isooctyl acrylate, lauryl acrylate, stearyl acrylate. Tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3-
Chloro-2-hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, acryloyl morpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropyl Acrylamide,
N, N-dimethylaminoethyl acrylate, phenoxyethyl acrylate, butoxyethyl acrylate,
Nonylphenoxyethyl acrylate, tetraethylene glycol-4-nonylphenyl ether acrylate, decaethylene glycol-4-nonylphenyl ether acrylate, dicyclopentenyl acrylate,
Dicyclopentenyloxyethyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-
Ethylhexyl methacrylate, isoamyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
2-hydroxy-3-phenoxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, N, N-dimethylaminomethyl methacrylate,
N, N-dimethylaminoethyl methacrylate, N, N
-Diethylaminomethyl methacrylate, N, N-diethylaminoethyl methacrylate, phenoxyethyl methacrylate, nonylphenoxyethyl methacrylate, tetraethylene glycol-4-nonylphenyl ether methacrylate, decaethylene glycol-4-
Nonyl phenyl ether methacrylate, tricyclo [5.2.1.0 ^{2, 6]} decanyl methacrylate, glycidyl methacrylate, 2-methacryloylethyl diisocyanate -, tri ethylene glycol diacrylate,
Tetraethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexane di-
Diacrylate, dimethylol tricyclodecane diacrylate, tripropylene glycol diacrylate, hexapropylene glycol diacrylate, 2-
Hydroxy-1-acryloxy-3-methacryloxypropane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol-
Rudimethacrylate, 1,4-butanediol-dimethacrylate, 1,6-hexanediol-methacrylate, trimethylolpropane trimethacrylate, ethylene oxide-modified trimethylolpropane triacrylate, dipentaerythritol hexaacrylate,
Urethane oligomer [trade name: U-4HA, U-6H
A, U-200AX, U-340AX, U-324A,
U-1084A, U-15HA, U-6LPA (manufactured by Shin-Nakamura Chemical Co., Ltd.), EB220, EB1290K (Daicel
U.S.B.).

The water and / or alcohol that can be used in the present invention dissolves the metal salt, acts to uniformly ionically cross-link the metal salt to the chlorinated polyolefin, and prevents the composition from gelling. It is added for the sake of safety. Therefore, those which can be distilled off when the composition is dried after application are preferred. Examples include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2.
-Propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,
3-methyl-1-butanol, 1-hexanol, 2-
Hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol , 4-methyl-2-
Pentanol, 1-heptanol, 2-heptanol,
3-heptanol, 2-methyl-2-hexanol, 2
-Methyl-3-hexanol, 5-methyl-2-hexanol, 4-methyl-3-heptanol, 6-methyl-
Examples thereof include 2-heptanol, 1-octanol, 2-octanol, 3-octanol, ethylene glycol, and propylene glycol.

The polymerizable composition of the present invention comprises the above components, and can be polymerized by heating or even by light. In polymerization by light, it is preferable to add an organic ionic dye compound which sensitizes by light to a composition comprising the above components. When an organic ionic dye compound is added,
It is preferable to use the above-mentioned organic boron compound or organic azobis compound as the radical initiator. The light sensitizes the organic ionic compound, which can easily radicalize the organic boron compound or the organic azobis compound. Organic ionic dye compounds include organic cationic compounds and organic anionic compounds, and both can be used.

Representative examples of the former are polymethine dye compounds, diphenylmethane dye compounds, and triphenylmethane dye compounds, and representative examples of the latter are azo dye compounds. As the composition of the present invention, those appropriately selected from these groups can be used alone or in combination of two or more. Examples of the above-mentioned organic ionic dye compounds that can be used for the purpose of the present invention are described in, for example, "Dye Handbook" edited by Okawara, Kodansha, 147-233.
Page 345-417. Examples of organic ionic dyes particularly suitable for the purposes of the present invention are listed in Table 1 together with their maximum absorption wavelength (λmax). However, it goes without saying that the present invention is not limited to these dyes. The compounds in Table 1 are as follows. (1) 1,1,5,5-tetrakis- (4-diethylaminophenyl) pentadienylium n-butyltriphenylboron (2) 1,1,5,5-tetrakis- (4-diethylaminophenyl) pentadi Enilium p-toluenesulfonic acid (3) Crystal violet (4) Rhodamine B (5) Methylene blue (6) Congo red

[0017]

[Table 1]

In the composition of the present invention, a chlorinated polyolefin, a metal salt, a radical initiator and a polymerizable functional group 1
The mixing ratio of the compound having at least one compound and water or / and alcohol is not particularly limited, but the metal salt is in the range of 0.01 to 20 parts by weight per 100 parts by weight (solid content) of the chlorinated polyolefin. , More preferably 0.
1 to 10 parts by weight, 0.05 to 2 radical initiators
0 parts by weight, more preferably 0.1 to 10 parts by weight, the compound having one or more polymerizable functional groups is in the range of 5 to 200 parts by weight, more preferably 10 to 100 parts by weight. The amount of water and / or alcohol is within the range of 0.5 to 3000 parts by weight, more preferably within the range of 2 to 1500 parts by weight. When the organic ionic compound is contained, the solid content of the chlorinated polyolefin is 100%.
0.1 to 10 parts by weight, preferably 0.2 to 10 parts by weight
5 to 5 parts by weight.

The polymerizable composition of the present invention exhibits strong adhesiveness even at high temperatures, for the following reasons. By adding metal salt, chlorinated polyolefin decomposes over time to absorb the hydrogen chloride generated and prevent the adhesive from deteriorating, and replace the desorbed chlorine atom to prevent the decomposition of chlorinated polyolefin, Crosslinking of the chlorinated polyolefin via the substituted metal improves thermal stability, so that strong adhesiveness can be obtained even at high temperatures. In addition, for chlorinated polyolefins having an acid value of 2 mgKOH / g or more, in addition to the above-described actions, the metal salt is ion-bonded to a substituent having an acid value to form ionic crosslinks, thereby improving heat resistance. Strong adhesion can be obtained even at high temperatures. The addition of water or alcohol has the effect of promoting the above-described reaction of the metal salt, has the effect of preventing the adhesive from gelling due to ionic crosslinking, and has the effect of improving storage stability.

The polymerizable composition of the present invention may contain, if necessary, a pigment, an ultraviolet absorber, a thickener, a thixotropic agent, a suspending agent, a matting agent, a softening agent, an antioxidant, an elastomer, a tackifier, and an organic amine. Compounds, solvents and the like can be added. Since the visible light or near-infrared light is used for the polymerization of the composition of the present invention even in the case of photopolymerization, the polymerization is not hindered by the addition of an ultraviolet absorber. The above components are mixed and stirred to form a composition. In order to preserve this, it is only necessary to keep the sun and the like out. The polymerizable composition of the present invention can be used for applications such as screen printing, lithographic printing, letterpress printing, metal surface processing, fillers (sealing agents) such as inks, paints, adhesives, and putties. Materials and products to which these uses are applied include synthetic resin molded products, metals such as steel, ceramics such as glass, and other materials without any particular limitation.
It may be reinforced by metal fibers, carbon fibers, or the like. The synthetic resin molded article may further contain additives such as a filler (talc, silica gel, alumina, calcium carbonate, and the like), an antioxidant, a softener, an antistatic agent, an ultraviolet absorber, a dye, and a pigment. As the shape of these materials and products, various shapes such as plates, films, sheets, tapes and cloths can be used.

As described above, the composition of the present invention can be applied to various molded articles and the like. Among them, polyolefin molded articles, which have conventionally been difficult to directly adhere, and vinyl chloride molded articles having a high affinity for chlorinated polyolefins. And an ABS (acrylobutadiene-styrene copolymer) molded article. For example, the adhesive is particularly effective as an adhesive for a material having at least one of these molded articles. The polymerization composition of the present invention, in the case of photopolymerization, is polymerized with high sensitivity when irradiated with light in the visible or near infrared region. , LEDs, sunlight and the like can all be used. The light intensity and the irradiation time are experimentally determined in consideration of the light transmittance of the adherend, the light sensitivity of the adhesive layer, the thickness, and the like. This composition does not require a physical or chemical treatment surface such as corona discharge, plasma treatment, gas flame treatment and chemical treatment or pliers treatment, and does not use ultraviolet rays often used for photopolymerization reaction during polymerization, It has the advantage that man-hours, equipment and security measures are small. The polymerizable composition of the present invention is also polymerized by heat. The heating temperature is 80-10
The temperature may be set to about 0 ° C.

[0022]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples. The names (trade names) and contents of the components used in the following examples are shown below. Carboxylic acid-modified chlorinated polyolefin: Supercron S-699 (chlorination rate 2.7%, acid value 2
0 mg KOH / g, toluene / butyl acetate = 80/20 solution having a solid content of 40% by weight) Supercron 892 L (chlorination rate 22%, acid value 19 m)
gKOH / g, toluene solution having a solid content of 20% by weight) Supercron 842LM (chlorination rate 20%, acid value 30)
mgKOH / g, toluene solution having a solid content of 20% by weight) Hardlen CY-9122P (chlorination rate 21%, acid value 3)
7 mg KOH / g, adjusted to a toluene solution having a solid content of 25% by weight) Plastic molded article: polypropylene of a propylene block copolymer (MK-459B, manufactured by Nippon Polyolefin Co., Ltd .; hereinafter, referred to as "MK4
59B ") Polyvinyl chloride coating foamed polypropylene on one side (Toray's polypropylene pef, hereinafter referred to as" PPF ") Light source: Infrared lamp (IR100V375WH, manufactured by Toshiba Lighting & Technology Corp., hereinafter referred to as" IR lamp ")

Evaluation of Adhesion and Adhesion Each of the above components was mixed to produce an adhesive composition of the following examples. Using the composition of each example, a propylene molded product MK459B was bonded to the PPF molded product (PPF molded product).
Was adhered to the foamed polypropylene side) and photopolymerized to conduct an adhesion test. 0.08 g of each composition is 12.5 c in length
m, a width of 2.5 cm, a thickness of 2 mm, and a test piece of a propylene molded article of 4 cm × 2.5 cm from one end,
After drying at 0 ° C. for 2 minutes, it was left at room temperature for 5 minutes. A PPF test piece having the same length and width as that of the above test piece and a thickness of 3 mm was heated at 130 ° C. for 10 minutes and stacked, and 0.5 kg / c
and pressed for 10 seconds at a pressure of m ^2. It left at room temperature for 3 minutes after crimping. After standing, light from an IR lamp was applied for 3 minutes from a distance of 10 cm from the polypropylene molded body side (Example 6 containing no pigment).
Was irradiated for 6 minutes), and the composition was photopolymerized and provided to an adhesive test piece. In the adhesion test, the PPF piece of the above test piece where the adhesive was not applied was bent at 90 ° (perpendicular to the other polypropylene molded body), and a 200 g load was applied to the bent piece at a temperature of 80 ° C for 24 hours. The degree of peeling was measured when it was applied to Table 2 shows the results. 180 ° peel adhesion at a temperature of 80 ° C. (pulling speed is 2
0 cm / min) was measured according to JIS K6854. Table 2 shows the results.

(Example 1) Component addition amount (parts by weight) Supercron S-699 (chlorinated polyolefin) 100 Magnesium oxide (metal salt) 1.6 Zinc oxide (metal salt) 1.0 Tetra n-butylammonium n -Butyltriphenyl 1.6 boron (radical initiator) tricyclo [5.2.1.0 ^2,6 ] decanyl acrylate 15 (polymerizable compound) acryloylmorpholine (polymerizable compound) 18 water 0.2 ethanol (alcohol) -L) 100 1,1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye) (The compounding amount includes the solvent. The same applies hereinafter.)

(Example 2) Component addition amount (parts by weight) Supercron 892L (chlorinated polyolefin) 100 Magnesium oxide (metal salt) 1.6 Zinc oxide (metal salt) 1.0 Tetra n-butylammonium n-butyl Triphenyl 1.6 boron (radical initiator) dicyclopentenyl acrylate (polymerizable compound) 15 acryloylmorpholine (polymerizable compound) 18 water 0.2 ethanol (alcohol) 100 1,1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye)

(Example 3) Component addition amount (parts by weight) Hardlen CY-9122P (chlorinated polyolefin) 100 Magnesium oxide (metal salt) 1.6 Zinc oxide (metal salt) 1.0 Tetra n-butylammonium n- Butyltriphenyl 1.6 boron (radical initiator) dicyclopentenyl acrylate (polymerizable compound) 15 acryloylmorpholine (polymerizable compound) 18 water 0.2 ethanol (alcohol) 100 1,1,5,5-tetrakis- ( 4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye)

(Example 4) Component addition amount (parts by weight) Supercron 892L (chlorinated polyolefin) 100 Magnesium oxide (metal salt) 1.6 Zinc oxide (metal salt) 1.0 Tetra n-butylammonium n-butyl Triphenyl 0.8 boron (radical initiator) lauroyl peroxide (radical initiator) 1.2 dicyclopentenyl acrylate (polymerizable compound) 15 acryloylmorpholine (polymerizable compound) 18 water 0.2 ethanol (alcohol) 100 1 , 1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye)

(Example 5) Component addition amount (parts by weight) Hardlen CY-9122P (chlorinated polyolefin) 100 Magnesium oxide (metal salt) 1.6 Zinc oxide (metal salt) 1.0 Tetra n-butylammonium n- Butyltriphenyl 0.4 Boron (radical initiator) 2,2'-azobis (2,4-dimethylvaleronitrile) 2.0 Dicyclopentenyl acrylate (polymerizable compound) 15 Acryloylmorpholine (polymerizable compound) 18 Water 0 0.4 ethanol (alcohol) 75 1,1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye)

(Example 6) Component addition amount (parts by weight) Supercron 892L (chlorinated polyolefin) 100 Magnesium oxide (metal salt) 0.8 Zinc oxide (metal salt) 0.5 Parloyl L (radical initiator) 2 Isobornyl acrylate 20 Water 0.5 Ethanol 100

(Comparative Example 1) Component addition amount (parts by weight) Supercron S-699 (chlorinated polyolefin) 100 tetra-n-butylammonium n-butyltriphenyl 1.6 boron (radical initiator) tricyclo [5.2 .1.0 ^2,6 ] decanyl acrylate 15 (polymerizable compound) acryloylmorpholine (polymerizable compound) 18 1,1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n- Butyltriphenylboron (dye)

(Comparative Example 2) Component addition amount (parts by weight) Supercron 892L (chlorinated polyolefin) 100 tetra n-butylammonium n-butyltriphenyl 1.6 boron (radical initiator) dicyclopentenyl acrylate (polymerizable) Compound) 15 acryloylmorpholine (polymerizable compound) 18 1,1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye)

Comparative Example 3 Component Addition Amount (parts by weight) Hardlen CY-9122P (chlorinated polyolefin) 100 Tetra n-butylammonium n-butyltriphenyl 1.6 Boron (radical initiator) Dicyclopentenyl acrylate (polymerization) Compound) 15 acryloylmorpholine (polymerizable compound) 18 1,1,5,5-tetrakis- (4-diethylaminophenyl) 0.4 pentadienylium n-butyltriphenylboron (dye)

[0033]

[Table 2]

In Examples 1 to 6, the oxidation was 2 mgKOH / g.
A polymerizable composition comprising the chlorinated polyolefin, metal salt, radical initiator, compound having one or more polymerizable functional groups, and water and / or alcohol.
Table 2 shows that in any of these examples, the polypropylene molded body was not subjected to surface treatment by light irradiation for a short time, and had a strong adhesiveness to the polypropylene molded body even at an environment of a temperature of 80 ° C. It indicates that Also,
In any of these embodiments, P
This is a material destruction of PF, indicating that it has a strong peel strength with respect to the polypropylene molded article.

[0035]

The polymerizable composition of the present invention comprises a chlorinated polyolefin, a metal salt, a radical initiator, a compound having at least one polymerizable functional group, water and / or an alcohol and optionally an organic compound. Since it contains an ionic dye compound, it can be directly applied to plastic molded products without surface treatment (especially for polyolefin molded products, corona discharge, plasma treatment, gas flame treatment, chemical treatment, etc.) Can be directly applied to the surface of the molded article without subjecting the molded article to surface treatment such as physical treatment, chemical treatment, or primer treatment), and can be adhered even by short-time light irradiation. Further, the polyolefin laminate formed by bonding using the polymerizable composition has a strong bonding strength even at a high temperature. In addition, since it is different from the conventional two-liquid type, the complexity of adjusting the adhesive and the complexity of the line cleaning can be eliminated, so that the work efficiency and the process can be simplified. Further, since the polymerizable composition of the present invention does not use ultraviolet rays even if it is photopolymerizable, it can be applied to materials which cannot be polymerized with ultraviolet rays even if the plastic molded article contains an ultraviolet absorber. In the present invention, polymerization adhesion and the like can be performed on a polyolefin molded article without surface treatment, but it goes without saying that a polyolefin molded article with a surface treatment may be used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 151/00 C09J 151/00

Claims (6)

[Claims] 1. A polymerizable composition comprising a chlorinated polyolefin, a metal salt, a radical initiator, a compound having at least one polymerizable functional group, and water and / or an alcohol. 2. A polymerizable composition comprising a chlorinated polyolefin, a metal salt, a radical initiator, a compound having at least one polymerizable functional group, an organic ionic dye compound, and water and / or an alcohol. . 3. The polymerizable composition according to claim 1, wherein the chlorinated polyolefin is modified. 4. The polymerizable composition according to claim 1, which is a chlorinated polyolefin having an acid value of 2 mg KOH / g or more. 5. An adhesive comprising the polymerizable composition according to claim 1. 6. A laminate in which at least one of the molded articles to be bonded is a polyolefin, polyvinyl chloride, or ABS molded article, using the adhesive of claim 5.