JPS58162640A - Coating composition for polyolefin plastic - Google Patents

Abstract

PURPOSE:To provide the titled composition curable rapidly by the irradiation with actinic energy radiation, and forming a coating film having excllent adhesivity to polyolefin plastics, etc., by compounding a chlorinated polyolefin resin to a monomer containing polymerizable unsaturated group. CONSTITUTION:The objective composition is prepared by uniformly mixing (A) 10-95wt% of a monomer containing two or more polymerizable unsaturated groups (preferably neopentyl glycol diacrylate, etc.), (B) 3-50wt% of a monomer containing one polymerizable unsaturated group (preferably glycidyl acrylate, etc.), (C) 2-50wt% of a chlorinated polyolefin resin (preferably a chlorinated polyethylene resin having a chlorine content of 50-80wt% and an average molecular weight of 10<4>-10<5>), and if necessary, (D) a photopolymerization initiator (e.g. benzoin). EFFECT:The composition gives a coating film having excellent solvent resistance, flexibility, curability, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for polyolefin plastics, and more particularly to a composition for polyolefin plastics that is cured by active energy F-irradiation: an adhesive, a printing material, or a material for J-type durables. The present invention relates to a coating composition useful as a coating composition.

Polyolefin plastics such as polyethylene and polypropylene are widely used in films and molded products. However, since these do not have polar or functional groups in their molecules, printing, adhesion, laminating tenter, sheet sealing, etc. of these films are difficult to achieve.
However, it was also difficult to adhere, paint, and print the molded product.

Conventionally, when applying adhesives, printing materials, paints, etc. to polyolefin plastics, the surface of the plastic was treated in advance with gas flame, acid treatment, coagulation, etc. in order to impart adhesive strength. However, the operation was complicated and the adhesion strength did not improve sufficiently.In addition, isocyanate-cured epoxy resin paints, chlorinated polypropylene resin paints, etc. are known as paints for polyolefin plastics. All of these are organic solution types that are formed at room temperature or by heating, but all of them do not have sufficient adhesion to the plastic, and their solvent resistance and curing properties are also unsatisfactory. Furthermore, as a coating method for polyolefin thread plastic materials, Japanese Patent Publication No. 53-8743 and Japanese Patent Publication No. 56-5777 disclose that unsaturated bond-containing organic W resin, two or more vinyl groups in one molecule, and a compound having one vinyl group in one molecule as main components, and a paint in which the base material is blended with a polymerizable unsaturated compound having a hydroxyl group and chlorine in one molecule. It is also known to apply a coating to the plastic and harden it by irradiating it with electrons, but in either case, the adhesion to the plastic is unsatisfactory from a practical standpoint, and the flexibility of the coating film is also insufficient. Furthermore, since at least IOMrad's electron-irradiation system is required to saponify the M1 film, it has the disadvantage of increasing power consumption and making it difficult to speed up the line speed of the coating process. are doing.

Therefore, in view of the above-mentioned situation, the present inventor conducted intensive research in order to eliminate these O defects, and as a result, a composition in which a chlorinated polyolefin resin was blended with a T-summer having a polymerizable unsaturated group was found to be an active energizer. We have discovered that it cures extremely quickly (based on biochemical technology) and forms a film that has significantly superior adhesion to polyolefin plastics, solvent resistance, flexibility, and hardening properties compared to conventional plastics. The present invention was completed based on this fact.

That is, the present invention provides (#) t having two or more polymerizable unsaturated groups in one molecule.
Tsumar - 10 to 95 weight (-) 1 polymerizable unsaturated group in one molecule (Tsum - 3 to 50 weight) and (t) Chlorinated polyolefin resin 2 to 50 weight), and The present invention relates to a coating composition for polyolefin plastics, which is characterized in that a photopolymerization initiator is added if necessary.

The present invention is a coating composition which is applied to the surface of a polyolefin plastic under irradiation with active energy and cured.
This is due to the combination of chlorinated polyolefin resin.

As a result, the composition cures very quickly when irradiated with active energy, and the cured film formed has excellent adhesion to acid plastics, solvent resistance, flexibility, hardenability, etc. It is. The reason for this is still unclear, but chlorinated polyolefin resin has excellent affinity with the plastic, and it may be that when irradiated with active energy 114-, hydrogen and chlorine abstraction reactions occur, causing polymerization. It is presumed that the crosslinking reaction with the hexamer having an unsaturated group simultaneously reacts with the plastic to be treated, and the chemical bonding between the coating and the plastic has a large effect.

In the present invention, the term "coating composition" refers to a composition that can be applied to polyolefin plastics, such as adhesives, paints, and printing inks, that may substantially coat at least one surface of the plastics. be.

Each component constituting the coating composition of the present invention will be explained below.

(#) T-mers having two or more polymerizable unsaturated groups in one molecule are di-, tri-, or but-5emole compounds, such as I thyrecylicol diacrylate, ethylene: JJ) Recall dimethacrylate 1 diethyl: J glycol diacrylate S diele Preliminary: Jj recall dimethacrylate, triethylene glycol diacrylate, tri-I ethylene glycol dimethacrylate 1 tetraethylecylicol diacrylate 1 det 5 I-regi glycol dimethacrylate, poly I ethylene glycol diacrylate 1 volume preresin glycol dimethacrylate 1 bottle rental glycol diacrylate, polyethylene glycol dimethacrylate, Otori, 3-butanediol diacrylate S 1.3- Butanediol dimethacrylate, 1,4-butanediol diacrylate, 1.
4-butasidiol dimethacrylate, 1.6-beef sashidiol diacrylate, 1.6-beef sanadiol dimethacrylate, neopentyltalicol diacrylate or dimethacrylate, trimethyl 0-0
Bashi triacrylate or trimethacrylate -
Pesitaerythritol triacrylate or trimethacrylate 1 A compound obtained by reacting acrylic acid or methacrylic acid with an adduct of pesitaerythritol tetraacrylate or tetramethacrylate and suphenol A and ethylene oxide or ethylene oxide, Draw with a polyisocyanate compound (e.g. hesylmethylethyl diisocyanate, tolylene diisocyanate, etc.)? Reaction products of diazyl(meth)acrylate (for example, dipropyl(meth)acrylate in dihydro-dipropyl(meth)acrylate in dihydro, etc.) and trimethyyl(meth)acrylate and trimethyyl(meth)acrylate with trimethyl(meth)acrylate in a ratio of 3 Acrylic acid to 1v of reactant with moles at 5℃
Examples include products obtained by reacting In the present invention, among these, 1.6-hemosacidiol diacrylate, neopesityl glycol diacrylate, 1 trimethyl glycol triacrylate, and the above trimethyyl glycol ratio Particularly preferred are products obtained by reacting a reaction product with beef side with acrylic acid, such as pentaerythritol triacrylate.

These T-summers may be used alone, or two or more types may be used in combination.

(b) Seven polymers having one polymerizable unsaturated group in one molecule; Examples of such seven polymers include carboxylic group-containing unsaturated seven polymers such as acrylic acid and methacrylic acid N-cricidyl acrylate) Acrylic acid or methacrylic acid such as chrycidyl group-containing unsaturated salts such as chrycidyl methacrylate; (C2-C,) Ester Polyethylene 7 glycol heptanoacrylate 1 Polyethylene 7 glycol methacrylate; Monoester of acrylic acid or methacrylic acid such as methacrylate and polyethylene glycol or polypropylene glycol; acrylic acid, ethyl acrylate, acrylic acid, isopropyl acrylate, acrylic acid Butyl 1 to acrylic acid, 1 to 1 acrylic fIII, 2 to ethyl, octyl acrylate - lauryl acrylate 1
Acrylic acid syl 0 to 10 syl 1 methyl methacrylate, 1 thyl methacrylate 1 methyl methacrylate 1 ethyl methacrylate Oe&-butyl methacrylate 1 to methacrylic acid (medium syl) to ethyl methacrylate 2 ethyl methacrylate 1 octyl methacrylate ~Lauryl methacrylate, methacrylate 0
Acrylic acid or methacrylic acid in alcohol (C□~'ia) or Schiff 0 alcohol ester;
Other additives include styrene, vinyl tornidine, methylstyrene, vinegar Im! vinyl, vinyl chloride,
Vinylisobutydiether 1 Acrylic 0 Nitrile 1 Methacrylic 0 Nitrile 1 Acrylamide 1 Methacrydiamide 1 Adduct of acrylic acid or methacrylic acid of lucridyl ether in alcohol Vinyl bihydride 5, dicyclic 0 Diethyl (meth)acrylate in pectenyl ε-Cub 0 lactosilic acid sialyl (meth)acrylate, tetrashydrofurfuryl acrylate, 1phenolic diethyl acrylate, the above acrylic acid or methacrylic acid ester + sialyl ester and aliphatic dibasic IM ! (For example, heptalytic adducts with hepatic acid, azizic acid, dimeric acid, heptabasic acid, acelaic acid, etc.).

In the present invention, among these, 0% bovine diethyl acrylate 1tallycidyl acrylate tetrahydrofurfuryl acrylate 1vinyl 20lydoxy, 0% bovine diethyl acrylate and an approximately heptadyl adduct of azidisic acid, etc. is particularly preferred.

These T-mers are appropriately selected depending on the desired physical properties, and each may be used alone or two or more types may be used in combination.

(C) Chlorinated polyolefin resin Examples of the chlorinated polyolefin resin used in the composition of the present invention include chlorinated polyolefin resin, chlorinated polyolefin resin, chlorinated polyolefin resin, and chlorinated polyolefin resin. Examples include copolymers.

That is, suitable chlorinated polyethylene resins have a chlorine content of 10 to 80% by weight, preferably 50 to 80% by weight, and a number average molecular weight of 5,000 to 200,000, preferably 10,000 to 100,000. . In addition, suitable chlorinated polyp resins have a chlorine content of 1O to 80% by weight, preferably 50 to 80% by weight, and a number average molecular weight of 5,000 to 100,000, preferably 1oooo to 80,000. However, the stereoregularity can be either isotactic or atactic.

If the chlorine content is less than 10% by weight, the compatibility with the ingredients listed above (-) and (1) may decrease; if the chlorine content is more than 80% by weight, the adhesion with olefin-based plastics may decrease. Also, the number average molecular weight is 5.
If it is smaller than 000, the physical strength of the formed cured film may decrease, and if it is larger than the above range, the viscosity of the composition may become high, making it difficult to handle.

In the present invention, these chlorinated polyolefin resins can be used alone or in combination of two or more, and the above (
-) and (h'') components are excellent.

The composition of the present invention has the above-mentioned components (j), (A), and (C) as essential components, and the composition ratio of each of these components is (
11), (the total of the season and component (C) is 100 weight ≦, component (a) is 10 to 95 weight ≦, preferably 50
~85wt≦, Cb) component is 3-50wt-1, preferably 5-20wt-1 and Cl) component is 2-50wt-1,
Preferably it is in the range of 10 to 30 weight. When the (-) component decreases by 10% by weight, the curability of the coating decreases,
On the other hand, if the weight increases by more than 95%, the flexibility and adhesion of the coating decrease. Also, if the amount of component (b) is reduced by 3 - 10% by weight, the flexibility of the coating will be reduced, while if it is increased by 50% by weight, the curability and adhesion will be reduced. Furthermore, when the (r) component is reduced by 2 weight, the adhesion decreases;
Therefore, in order to achieve the object of the present invention, components (a), <4>, and (e) must be controlled within the above ranges. It is necessary to mix and mix within the above range, and the object of the present invention cannot be achieved outside the above range.

Photopolymerization initiator The coating formed from the composition of the present invention is cured by irradiation with active energy f- such as electron beams and ultraviolet rays.
It is necessary to add a photopolymerization initiator in advance to the composition consisting of (#) and <1> component.

As the photopolymerization initiator, a normal photopolymerization initiator that is excited by ultraviolet irradiation and generates radicals is used, such as beniJ%), besyri methyl ether, besili ethyl ether 1 benlyin n -Propyl ether ~ Benryishisozu0jiru ether 1 besilishin -
Butyl ether, penrifenone 1 unit - methylbenrifeno: J1Σ largaton, acetophenone, 2-ri 0
Examples include 0thio10santhone\anthratenone, 2-methylacytratenone, 1 phenyl disulfide, 2-nide 0 fusiolene, and the like. These photopolymerization initiators can be used alone or in combination of two or more.

The blending amount thereof is preferably in a ratio of 0.1 to 10 weight ≦ of the total amount of the above (#) and (1) component.

Furthermore, in the composition of the present invention, a photosensitization accelerator may be used in combination with the photopolymerization initiator in order to promote the photopolymerization reaction by the photopolymerization initiator. Examples of photosensitization accelerators include tertiary amines such as 1-triethylamino-1-triethanolamine and 2-dimethylaminoethanol, acylphosphines such as triphenyl phosphin, thioethers such as 1β-ocitalicol, etc. . These photosensitizers can be used alone or in combination of two or more. The blending amount thereof is preferably at a ratio of the total amount of components (#), (#) and (C) above 00.1-go weight.

The composition of the present invention is as described above.
The (-) component is essential, and the (B) component may be used in combination as necessary. Furthermore, pigments (extender pigments, colored pigments, metallic pigments, magnetic metal powders, etc.) and dyes commonly used in the composition can also be used in combination, and low boiling point (
A small amount of organic solvent (below 150°C) may also be used.

The C)111 composition of the present invention can be easily obtained by uniformly mixing the above-mentioned components using a mixing/dispersing machine used in producing paints.

Furthermore, the composition of the present invention can be used, for example, with polyethylene resin,
It can be used as adhesives, paints, and printing plates for polyolefin plastics such as Volip 0ji resin. That is, a film containing the plastic as a main component,
Adhesives for bonding sheets, plates, and molded bodies to films, sheets, plates, and molded bodies of the same or different types (e.g., plastics other than polyolefin plastics, non-materials such as metal and glass, wood, etc.) It is useful as It is also useful as a printing ink and paint for printing and painting polyolefin plastics.

The O composition of the present invention can be coated on polyolefin plastics using an 0-L coater, a 9-TESIF 0-coater, a dip coater, an electrostatic coater, a spray gun, a conventional printing machine, and the like. The coating thickness is preferably 3 to 200 microns.

Since the composition of the present invention has excellent adhesion to polyolefin-based plastics, there is no need to pre-treat the surface of the plastic with corona discharge treatment, oxidizing agent treatment, alkali treatment, etc.; There is no problem even if the surface is treated.

The coating made of the oma product of the present invention can be cured by irradiating the coating with active energy directly or through the object to be coated. Examples of active energy f-rays include electron beams and ultraviolet rays, and any of them may be used.

Examples of electron beam generation sources include equipment such as 0ft ils, pan de Klaaf type, resonant transformer, power supply equipment, and insulated core transformer 4111. Taif=)o:
These include JILS linear filament lids and high-rise devices. Electron beam irradiation conditions-1: There are no particular restrictions and can be arbitrarily selected depending on the shape of the object to be coated, but a dose of 0.5 to 20 mm is suitable. Even below is sufficient.

Examples of sources of ultraviolet irradiation include mercury rays, 10 tons, 1 metal paralyte, sunlight, and the like. The irradiation conditions for ultraviolet rays are not particularly limited either, but it is desirable to irradiate for several seconds or more in air or in an inert gas atmosphere.

In particular, when irradiating in air, it is preferable to use a high-pressure mercury lamp.

Next, the content of the present invention will be explained in more detail with reference to Examples and Comparative Examples. Parts and weights in the examples refer to parts by weight and weight arcs unless otherwise specified.

Examples and Comparative Examples A composition applicable to the present invention (Example 1) was prepared by uniformly mixing and dispersing the components in the amounts listed in Table 1.
-10) and comparative compositions (Comparative Examples 1-9) were manufactured.

(Note) (Mine 1) A product name manufactured by Toagosei Chemical Industry Co., Ltd., which is a reaction product of trimethyyl 0-ru 0 bacy Ir nyl and diacrylic acid 3°C per diacrylic acid added. (*2) A product name manufactured by Toagosei Kagaku Kogyo ■, which is an isocytyl adduct of hydrochloride + siethi nyl acrylate and azitriic acid.

(113) Chlorinated polypropylene resin with a chlorine content of approximately 66% and a fine average molecular weight of approximately 10,000, manufactured by Demikokugun Palzu.

(*4) Product name made by Demi Kokusaku Pulp■, with a chlorine content of approximately 6
6≦, chlorinated polyp with a fine average molecular weight of about 20,000 0jireji IIWiI0 (flea 5) Product name made by Demikokusaku Pulp ■, chlorine content about 6
6-1 Chlorinated polyethylene resin with a number average molecular weight of about 40,000.

Ratio a example 10 Super Ku0 Shimu 406 20 parts sheet J Shimu
Proportional example 1 of a paint made by mixing 20 parts of chlorinated paraffin, 10 parts, and 50 parts of chlorinated paraffin! The composition of Example 1 was produced by replacing component (C) with an acrylic resin containing a polymerizable unsaturated group. The acrylic resin contains 26 parts of methyl methacrylate and 50 parts of ethyl acrylate.
Comparative Example 12 Component <1> in the composition of Example 4 was reacted with 15 parts of dimethacrylic acid per 100 parts of acrylic resin consisting of % and 24% lysidyl methacrylate.
This is a composition produced in place of acrylate.

Performance test results The compositions obtained in the above Examples and Comparative Examples were applied to a polyethylene film (thickness: 40 μm) using a reverse roll coater, and then a polyethylene film (thickness: 4 μm) was coated on the coated surface.
0μ) was laminated using a laminator, and then cured by irradiation with an electron beam or ultraviolet rays. The composition of Comparative Example 10 was coated without irradiation with active energy, but after evaporating the solvent (medium silica), it was heated to 130°C. Named Nate.

Table 2 JP-A-58-162640 CB) In Table 2, (*l) Adhesion: When laminating films by the method described above, leave areas where the composition is not coated, and after curing, The adhesion strength of the composition was tested by pulling each of the films on the painted area in opposite directions. The unit of numerical values in the table is #/155g. Incidentally, a value of 1.5#/1 or more indicates that the film itself has been destroyed.

(*2) Flexibility: polyp at? Len film (thickness μ)
Each of the above compositions was coated on one side of the screen to a cured film thickness of 10 seconds, and after being cured without lamination, the film was bent at an acute angle of 360° at 5°C with the film on the outside. The condition was observed.

(*3) Solvent resistance 2. Drop 5 cc of beef seal onto the coated surface of the sample obtained in the same manner as above (*2).
A cylindrical crow cup with an inner diameter of 23 mm and a depth of 2 cm was placed on top of the cup, and after being left at room temperature for 24 hours, the cow syrup was wiped and observed for solvent marks, blisters, discoloration, etc.

(Flea 4) Curability: IHMs obtained in the same manner as in (112) above were rubbed together to examine the presence or absence of tackiness.

(Mine 5) Indicates that it was cured by irradiation with an electron beam, and the title is 2 Mrmd (megarad).

(II6) Indicates that the material was cured by irradiating ultraviolet rays from a 120-watt high-pressure mercury lamp, the irradiation time was 1 second, and the distance was 13.

(that's all)

Claims (1)

[Claims] (a) t having two or more polymerizable unsaturated groups in one molecule
(A) consisting of 3 to 50% by weight of 3 to 50% by weight of 7 to 11% by weight (A) having one polymerizable unsaturated group in one molecule and <1> chlorinated polyolefin:/resin 2 to 501% by weight, and further 1. A coating composition for polyolefin plastics, which is further added with a photopolymerization initiator (Il/) if necessary.