JP3100675B2 - Hot melt composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hot melt adhesive,
The present invention relates to a hot melt composition used for a hot melt coating agent and the like. More specifically, the present invention relates to a hot melt composition exhibiting good adhesiveness to polyvinyl chloride, polypropylene, polyester, metal and the like.

[0002]

2. Description of the Related Art Hot-melt adhesives have an economical advantage in that they can be bonded instantaneously and at a high speed without using any solvent, so they are mainly used in the fields of bookbinding, packaging, woodworking, etc. Used in large quantities. In recent years, it has begun to be used in industrial fields such as automobiles and building materials. However, various adhesives have been studied for polyvinyl chloride, polypropylene, and polyester, which are not easily bonded.

For example, regarding polyvinyl chloride,
As the hot melt adhesive, only a polyester-based adhesive is used (JP-A-58-42458).
Chloroprene rubber, NBR, urethane (JP-A-60-2)
55882), and the use of a solution type adhesive based on polyester or the like has been the mainstream. However, polyester-based hot melt adhesives are not satisfactory in flexibility and hydrolysis resistance at low temperatures, and solution-type adhesives have problems such as solvent recovery and exhaust, so it is necessary to pay attention to the working environment. In addition, there was a disadvantage that the cost was high.

[0004] Regarding adhesion to polypropylene,
Ethylene-propylene rubbers, styrene rubbers such as SIS and SEBS, or those obtained by grafting maleic anhydride to these rubbers are used, but their performance is not sufficiently satisfactory. In addition, these adhesives have a problem that their adhesive performance to other adherends such as polyester and polyvinyl chloride is not sufficient. A method of applying an anchor coating agent such as polyethyleneimine, isocyanate, or polybutadiene to the surface of polypropylene to improve adhesiveness has also been performed, but there is a problem such as the use of a solvent.

Acrylics, polyurethanes, isocyanates and the like are used for bonding polyesters, but there are problems such as the use of solvents, adhesiveness, and price. Currently, hot melt adhesives such as polyvinyl chloride, polypropylene, polyester, etc., which are difficult to adhere to each other, and adhesives used for bonding these adherends to metals, are satisfactory. is not.

[0006]

SUMMARY OF THE INVENTION The present inventors have developed a highly polar adherend such as polyvinyl chloride, a low polar adherend such as polypropylene, or an engineering plastic such as polyester. As a result of studying a composition capable of hot-melt bonding to a material that is difficult to bond and bonding to a metal, a new formulation has been found. Accordingly, it is an object of the present invention to provide a novel hot melt adhesive composition.

[0007]

According to the present invention, there is provided an ethylene copolymer containing (A) 2 to 50% by weight of an unsaturated carboxylic acid ester, 30 to 95% by weight of ethylene and 3 to 20% by weight of carbon monoxide. 5 to 94% by weight of a polymer; (B) 50 to 94% by weight of a hydrocarbon rubber composed of a hydrocarbon polymer or copolymer; and (C) a hydrocarbon resin, a polyterpene resin, a rosin or the like.
A hot melt composition comprising 90 to 1% by weight of a tackifier resin selected from the group consisting of coumarone and indene-based resin .

The ethylene copolymer used in the present invention is:
It is a random copolymer of unsaturated carboxylic acid ester, ethylene and carbon monoxide. Here, the unsaturated carboxylic acid ester is preferably an α, β-unsaturated carboxylic acid ester,
As the α, β-unsaturated carboxylic acid component, acrylic acid,
Methacrylic acid, maleic acid and the like are used, and as the alcohol component constituting the ester, a linear or branched alcohol having about 1 to 10 carbon atoms is preferable, and specifically,
Methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, sec-
Butanol, n-hexanol, n-octanol, 2
-Ethylhexanol, n-decanol and the like are used. As such unsaturated carboxylic acid esters, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, (meth)
Examples thereof include n-butyl acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and dimethyl maleate. Among these,
In consideration of the low-temperature characteristics of the ethylene copolymer, it is preferable to use a primary ester of acrylic acid.

The proportion of each polymer component in the ethylene copolymer is such that the unsaturated carboxylic acid ester is 2 to 50% by weight,
Preferably 5 to 40% by weight, 30 to 95% by weight of ethylene, preferably 35 to 85% by weight, 3 to 2% of carbon monoxide.
0% by weight, preferably 5 to 15% by weight. With such a polymerization ratio, the compatibility with the hydrocarbon rubber and the tackifying resin is excellent, and the adhesion to polyvinyl chloride, polypropylene, polyester, and metal is also excellent.

[0010] When the content of carbon monoxide is less than 3% by weight, the adhesiveness becomes poor. On the other hand, if the content exceeds 20% by weight, the weather resistance of the ethylene copolymer deteriorates, so that the field of use thereof is restricted. Such an ethylene copolymer also includes a melt flow rate (1).
90 ° C., 2160 g load) is 0.1 to 3000 g / 10
Of the order of minutes. The above-mentioned ethylene copolymers are already well known, and generally have a reaction temperature of 150-2.
It is obtained by radical copolymerization of an unsaturated carboxylic acid ester, ethylene and carbon monoxide by a method of bulk polymerization under conditions such as 50 ° C. and a reaction pressure of 500 to 3000 kg / cm ² , and also in solution polymerization or emulsion polymerization. Manufacturing is possible.

The hydrocarbon rubber used in the present invention includes polybutadiene, styrene-butadiene copolymer, styrene-isoprene copolymer, butyl rubber, polyisobutylene, ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene-butene copolymer. -Propylene-butene copolymer, ethylene-butadiene copolymer, ethylene-propylene-
Butadiene copolymer, ethylene-propylene-1,4-
Hexadiene copolymer, ethylene - propylene - nor ball <br/> Runajien copolymer, propylene - butadiene copolymer, comprising a polymer or copolymer of a hydrocarbon such as Gore
It is a beam, preferably butyl rubber, polyiso blanking styrene,
Styrene-butadiene copolymer, styrene-isoprene copolymer, ethylene-propylene copolymer, ethylene-
Butene copolymer and ethylene-propylene-butene copolymer. The composition ratio, molecular weight,
The viscosity can be selected arbitrarily widely.

[0012] The tackifier resin used in the present invention is a carbonized resin.
Hydrogen resin, polyterpene resin, rosin or cumaro
This is an indene-based resin, which is already known in the hot melt adhesive field . <br/> aliphatic hydrocarbon resin is a hydrocarbon resin, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, such as scan styrene resins.

Examples of the aliphatic hydrocarbon resin include 1-
Butene, isobutylene, butadiene, 1,3-pentadiene, isoprene, etc. polymers and the like mainly composed of _C 4 -C ₅ mono- or di-olefins such as piperidine. Examples of the alicyclic hydrocarbon resin include Spent C ₄
-C ₅ fraction in the resin the diene component were polymerized after cyclization dimerization of the cyclic monomer is polymerized resins, such as resins obtained by nuclear hydrogenation of aromatic hydrocarbon resins include, such as cyclopentadiene Can be Examples of aromatic hydrocarbon resins include:
Examples thereof include resins mainly containing C _{9 to} C ₁₀ vinyl aromatic hydrocarbons such as vinyltoluene, indene, and α-methylstyrene. Examples of polyterpene resins include α-pinene polymer, β-pinene polymer, dipentene polymer, terpene-phenol copolymer, α-pinene-
Phenol copolymers and the like can be mentioned. Rosins are gum rosin, wood rosin, rosins such as tall oil and modified products thereof, and hydrogenated, disproportionated,
Those which have been subjected to modification means such as dimerization and esterification can be exemplified. Examples of rosin esters include esters such as ethylene glycol, diethylene glycol, glycerin, pentaerythritol and the like. Styrene-based hydrocarbon resins include polymers such as styrene, vinyltoluene, α-methylstyrene, and isopropenyltoluene. The above-mentioned tackifier resin may be a resin modified by grafting with maleic anhydride, maleic ester or the like.

Among these tackifying resins, rosins, terpene phenol resins, aromatic hydrocarbon resins, and styrene hydrocarbon resins are considered in consideration of the compatibility with the ethylene copolymer and the hydrocarbon rubber. It is preferred to choose from

The mixing ratio of the ethylene copolymer, the hydrocarbon rubber and the tackifying resin can be varied over a relatively wide range, but the total adhesive strength and compatibility with various adherends are taken into consideration. Then, (A) 5 to 94% by weight, preferably 10 to 70% by weight of the ethylene copolymer, (B)
5 to 94% by weight, preferably 10 to 70% by weight of hydrocarbon rubber
% By weight, (C) 1 to 90% by weight of the tackifying resin, preferably 5 to 60% by weight.

The viscosity of the composition of the present invention can be set arbitrarily widely. If the device to apply to the adherend is a conventional hot melt applicator, roll, etc.,
It is set to a low viscosity of 300,000 CPS or less (180 ° C.) and 300,000 CPS or more (180
° C). The setting of the viscosity of the composition includes (A) an ethylene copolymer, (B) a hydrocarbon rubber,
(C) It is set by changing the molecular weight of each tackifier and by changing the mixing ratio of (A), (B) and (C).

In the present invention, a copolymer of an unsaturated carboxylic acid ester and / or a vinyl ester and ethylene can be blended as an optional component to such an extent that the adhesiveness of the composition is not impaired. Such an ethylene copolymer can be blended for the purpose of improving the heat-resistant adhesiveness and reducing the cost. Examples of the ethylene copolymer of the optional component include an ethylene-methyl (meth) acrylate copolymer,
Ethylene-ethyl (meth) acrylate copolymer, ethylene-butyl (meth) acrylate copolymer, ethylene-
Ethylene / (meth) acrylate copolymers such as 2-ethylhexyl (meth) acrylate copolymer, ethylene / vinyl ester copolymers such as ethylene-vinyl acetate copolymer and ethylene-propenyl acetate copolymer And the like. The content of the ester monomer in these ethylene copolymers is preferably in the range of 5 to 50% by weight, particularly 10 to 45% by weight in consideration of compatibility, heat resistance and the like. The melt flow rate is preferably from 0.1 to 3000 g / 10 minutes.

The hot melt composition of the present invention may further contain a wax for the purpose of improving the melt fluidity. Specific examples of such waxes include petroleum waxes such as paraffin wax and micro wax, natural waxes such as wood wax, carnauba wax and beeswax, and synthetic waxes such as crystalline polyethylene wax, crystalline polypropylene wax, and atactic polypropylene. Among them, carnauba wax and beeswax are preferably used. If the compounding amount of the wax is excessively increased, the adhesive strength tends to decrease. Therefore, the compounding amount is 40% by weight or less, preferably 20% by weight in the hot melt composition.
It is better to do the following.

The hot melt composition of the present invention may contain an antioxidant, a weather stabilizer, a filler, a plasticizer, an oil and the like according to the purpose of use.

The composition of the present invention can be obtained by melt-mixing the components simultaneously or in any order. The mixing method is optional, using an extruder, an open roll mill, a Banbury mixer, a kneader, a kneader ruder, a method of mixing under mechanical mixing conditions using a melt mixing layer,
A method of mixing at the time of extrusion using a plurality of extrusion means such as an extruder and a hot melt applicator can be adopted.

The hot melt composition of the present invention thus obtained comprises polyvinyl chloride, polyvinylidene chloride,
Polyolefins such as chlorinated polyethylene, chloroprene rubber, halogenated olefin polymers such as PVC elastomers, polyethylene, polypropylene, polybutene, poly-4-methyl-pentene-1, ethylene- (meth) acrylate copolymers, etc. Resin, polystyrene, ABS, ethylene-vinyl alcohol copolymer, polyester, polyamide, polycarbonate, polyester elastomer, composition of these polymers, melamine resin, metal, wood, particle board, paper, cloth, natural and synthetic leather, And it can be used for bonding of synthetic resin foam and the like.

For bonding, conventionally used equipment for hot melt can be used. For example, various coating facilities such as a nozzle type hot melt applicator, a spray type hot melt applicator, a flat nozzle type hot melt applicator, a roll type coater, and an extruder type coater are used. Further, the hot melt composition of the present invention can be used as an adhesive for automobiles, building materials, furniture, electric and electronic parts, decorative articles, packaging materials and the like.

[0023]

The hot melt composition of the present invention exhibits excellent adhesion to many adherends, such as polyvinyl chloride, polypropylene and polyester, which are not easily adhered. Further, since it is excellent in flexibility at low temperatures and hydrolysis resistance, it can be expected to be used in various fields.

[0024]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The test method used in the present invention is as follows.

Method for preparing adhesive specimen : The hot melt adhesive composition was hot-pressed at 160 ° C. to prepare a 0.2 mm sheet. This sheet is sandwiched between adherends, and is sealed with a heat sealer at a seal width of 25 mm, a seal temperature of 120 ° C., a seal pressure of 1 kg / cm ² , and a seal time of 10 seconds.
It was cut into strips of m width.

Adherend for adhesion test : Soft PVC (hereinafter referred to as PV)
For C), a film having a DOP compounding amount of 40 parts by weight (with PVC as 100 parts by weight) and a thickness of 0.2 mm / was used. As the polypropylene (hereinafter referred to as PP), a film having a thickness of 0.2 mm was used. Polyethylene terephthalate (PET)
Used a Toray lumirror (0.1 mm). Aluminum (hereinafter Al) is commercially available soft aluminum (0.1 m
m) was used after being degreased with acetone.

Adhesive strength measuring method : T-peel strength was measured with a tensile tester at a crosshead speed of 300 mm / min. The measurement was performed at 23 ° C.

Example 1 Ethylene-n-butyl acrylate-carbon monoxide copolymer (n-butyl acrylate content 30% by weight, carbon monoxide content 10% by weight, melt flow rate 100 g / 10
Min) 40% by weight and butyl rubber (JSR Butyl 2)
68, Mooney viscosity ML _{1 + 3} 55 ° C. at 127 ° C. 55) 40% by weight and 20% by weight of rosin ester (Arakawa Chemical Superester A100) in a Labo Plast Mill (30C150 type Labo Plast Mill manufactured by Toyo Seiki Seisakusho) are used for 160.
C. for 20 minutes. Adhesive strength is PVC, PP, PE
3.5, 5.9, 5.3, respectively for T and Al
It was 6.2 kg / 25 mm.

Example 2 In Example 1, the same butyl rubber 2 as the same ethylene-n-butyl acrylate-carbon monoxide copolymer (60% by weight) was used.
Evaluation was carried out on a blend of 0% by weight and 20% by weight of the same rosin ester. Adhesive strength is PVC, PP,
4.6, 4.2, and 4. respectively for PET and Al.
5, 3.6 kg / 25 mm.

Example 3 In Example 1, the same butyl rubber 6 as the same ethylene-n-butyl acrylate-carbon monoxide copolymer 20% by weight was used.
Evaluation was carried out on a blend of 0% by weight and 20% by weight of the same rosin ester. Adhesive strength is PVC, PP,
2.7, 6.5, and 3 for PET and Al, respectively.
3, 4.7 kg / 25 mm.

Example 4 The same butyl rubber 1 as in Example 1 but with 40% by weight of the same ethylene-n-butyl acrylate-carbon monoxide copolymer
An evaluation was carried out for a mixture of 0% by weight and 50% by weight of the same rosin ester. Adhesive strength is PVC, PP,
4.0, 3.0, 4 for PET and Al, respectively.
It was 2, 3.4 kg / 25 mm.

Example 5 The same ethylene-n-butyl acrylate-carbon monoxide copolymer (60% by weight) and styrene-isoprene-block copolymer rubber (Califlex TR manufactured by Shell Chemical Co., Ltd.) as in Example 1 were used.
-1107) 20% by weight and aromatic hydrocarbon resin (Tackifier resin Mitsui FTR6100 manufactured by Mitsui Petrochemical) 20
% By weight in a Labo Plastomill at 160 ° C. for 20 minutes. The adhesive strength was 4.3, 4.1, 5.7 kg / 25 mm for PVC, PP, and PET, respectively.

Comparative Example 1 In Example 1, two components of an ethylene-n-butyl acrylate-carbon monoxide copolymer 80% by weight and a rosin ester 20% by weight were used. Adhesive strength is PVC, PP, PE
4.1, 2.0, 5.1, respectively for T and Al
It was 0.3 kg / 25 mm.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 53/02 C08L 53/02 57/02 57/02 73/00 73/00 93/00 93/00 93/04 93/04 C09J 109 / 00 C09J 109/00 123/22 123/22 125/02 125/02 145/02 145/02 153/02 153/02 157/02 157/02 193/00 193/00 193/04 193/04 (56) References JP-A-3-181557 (JP, A) JP-A-59-30843 (JP, A) JP-A-55-31893 (JP, A) JP-A-48-26228 (JP, A) JP-A-168057 (JP, A) JP-A-64-43552 (JP, A) JP-A-50-34087 (JP, A) JP-A-61-183343 (JP, A) JP-A-2-73828 (JP, A) Patent No. 2965589 (JP, B2) Japanese Patent Publication No. 7-10968 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 173/00 C09J 109/00-109/10 C09J 123 / 00-123/24 C09J 125/02-125/16 C09J 145/02 C09J 153/02 C09J 157/02 C09J 193/00 C09J 193/04 C08L 73/00 C08L 9/00-9/10 C08L 23/00- 23/24 C08L 25/02-25/16 C08L 45/02 C08L 53/02 C08L 57/02 C0 8L 93/00 C08L 93/04 C08G 67/02

Claims (2)

(57) [Claims] (1) An unsaturated carboxylic acid ester (A) having 2 to 5
(B) a hydrocarbon polymer or copolymer comprising 5 to 94% by weight of an ethylene copolymer containing 0% by weight, 30 to 95% by weight of ethylene and 3 to 20% by weight of carbon monoxide. (C) hydrocarbon resins, polyterpene resins, rosins, etc.
Or a hot-melt composition comprising 90 to 1% by weight of a tackifier resin selected from the group consisting of coumarone and indene-based resin . 2. The hot melt composition according to claim 1, wherein the hydrocarbon rubber is a polyisobutylene rubber.