JPH04255779A - Hot melt adhesive composition - Google Patents

Abstract

PURPOSE:To obtain a hot melt adhesive composition containing a thermoplastic high polymer, tackifier, wax and specific phosphate and having bonding property to metal having oil surface and rust proofing property to metal. CONSTITUTION:The objective adhesive composition containing (A) a thermoplastic high polymer, preferably butyl rubber having 20000-1500000 molecular weight or polystyrene resin, (B) tackifier, preferably stabilized rosin (ester) and/or (C) wax which is a crystal wax having >=130 deg.C softening temperature and further (D) 0.1-30wt.% phosphate expressed by formula I, formula II or formula III [R is 1-12C alkyl, (di)phenyl, benzyl(phenyl) or alpha-methylbenzyl(phenyl); R' is 2-4C alkylene or hydroxypropylene; m is 0-20; a is 1-6; b and c are 1-2; X is phytic acid; Y is phosphoric acid; Z is phosphorous acid].

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is a hot-melt adhesive composition that is most suitable for use in bonding or sealing with metals without pretreatment, and more specifically, in particular when used for bonding or sealing with metals on oil surfaces. The present invention relates to a hot melt adhesive composition that can be preferably used for difficult-to-adhesive plastic materials.

0002

[Prior Art] Hot melt adhesives have traditionally been used in various fields, and their industrial benefits are well known, and their use is increasing due to their instant adhesive properties and non-polluting properties. There is. However, when you look at the actual product, it shows good adhesion properties especially to metal materials on oil surfaces and hard-to-adhesive plastics such as soft vinyl chloride resin, polypropylene, polyethylene, and polycarbonate, and it also takes into account rust prevention properties for metals. A preferred hot melt adhesive composition has yet to be found. In particular, bonding with various metal steel sheets is performed in the automobile industry, home appliance industry, building material industry, and the like. For example, in the automobile industry, there is a demand for soft vinyl chloride resin packing and for fixing various plastic molded bodies to metal surfaces. In addition, in the field of home appliances, there are demands for fixing or sealing soft vinyl chloride resin coated wires, and demands for metal adhesion to other substrates. To meet these demands, solvent-based adhesives, epoxy adhesives, two-component acrylic adhesives, etc. have been used appropriately, and these adhesives are thermosetting adhesives that can adhere to oil surfaces. Also known as. However, in recent years, there has been an opportunity to reconsider hot melt adhesives, especially from the viewpoint of pollution-free and short-time bonding. In this case, the biggest problem to be solved is the problem of oil surface adhesion, and the current situation is that the development of a hot melt adhesive capable of oil surface adhesion is the strongest demand. On the other hand, conventionally known hot melt adhesives include polyamide hot melt adhesive compositions, polyester hot melt adhesive compositions, ethylene-vinyl acetate hot melt adhesive compositions, and rubber hot melt adhesives. agent compositions, etc. The former two hot melt adhesives are known as hot melt adhesives for bonding metals, fibers such as cloth, and plastics;
The latter two are widely known as hot melt adhesives for plywood and paper cartons. In either case, a certain degree of adhesion is possible with clean metal or metal that has been treated with a primer, but it is completely unsuitable as a metal adhesive for oil surfaces.

For example, Japanese Patent Publication No. 60-92379 discloses a hot melt adhesive for sealing which uses butyl rubber as a base polymer and contains a tackifier, wax, etc. as the main components; ",same"
50-8847'', hot melt adhesives using ethylene-vinyl acetate as a base polymer, and JP-A No. 50-8847''
0-10332'', JP Kosho ``44-9597'', etc., are hot melt adhesives using polyamide as a base polymer;
Hot melt adhesives using polyester as a base polymer are disclosed in Japanese Patent Application Laid-open No. 05727 and Japanese Patent Application Laid-Open No. 50-130830. In the technologies disclosed so far, when joining metals with a hot melt adhesive composition for metals, pretreatment is required, such as degreasing with a solvent or flame treatment for both degreasing and preheating. It was mandatory. In other words, the first major problem in the market is that there is a demand for hot melt adhesives that take advantage of the instant adhesive properties of hot melt adhesives and have excellent adhesion to oil surfaces without any pretreatment. . Secondly, in addition to oil surface adhesion performance, adhesion reliability with difficult-to-adhesive plastics such as polypropylene, acrylic, polyethylene, polycarbonate, acrylonitrile styrene resin, vinyl chloride resin, etc. is required. Thirdly, there is a need for the bond to have high long-term reliability, such as water resistance and long-term environmental compatibility, and resistance to deterioration in environmental exposure tests, etc., especially when adhering difficult-quality vinyl chloride. , there are demands for adhesives with low plasticizer migration to be highly reliable and to have excellent plasticizer resistance.

0004

[Problem to be solved by the invention] The main purpose is to obtain a hot melt adhesive composition suitable for highly reliable bonding without any pretreatment when bonding mainly metal materials. be. In other words, when untreated (without degreasing) oils used during metal surface treatment such as lubricating oil, rust preventive oil, and processing oil remain on the surface of metal materials, instant adhesive properties are obtained. The main objective is to provide a hot-melt adhesive composition that can be produced and exhibit sufficient adhesion reliability. More specifically, satisfying the above three requirements is to obtain a hot melt adhesive that is capable of achieving not only the above-mentioned oil surface adhesion, but also adhesion to difficult-to-adhesive plastics, and sufficiently high adhesion reliability. and/or to provide a hot melt composition that exhibits seal reliability.

[0005]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have made extensive studies and found that a hot melt adhesive composition containing a specified phosphoric acid ester is good. We have arrived at the present invention. That is, the present invention is as follows.

(a) A hot melt adhesive comprising a thermoplastic polymer, a tackifier and/or a wax, and a group of phosphoric esters represented by the following general formulas (1) to (3). One or more selected from 0.
A hot melt adhesive composition characterized by containing 1 to 30% by weight. [R-O-(R'O)m]a-X (1) [R-O-
(R'O)m]b-Y (2) [R-O-(R'O)
m]c-Z (3) (wherein, R has 1 to 1 carbon atoms
2 alkyl group, phenyl group, diphenyl group, benzyl group, benzylphenyl group, α-methylbenzyl group, α-
Methylbenzylphenyl group, R' represents an alkylene group having 2 to 4 carbon atoms or a hydroxypropylene group, m is 0
-20, a is an integer of 1 to 6, b and c are integers of 1 to 2, X is a phytic acid group, Y is a phosphoric acid group, and Z is a phosphorous acid group. ) (b) The hot melt adhesive composition as described in (a) above, wherein any one of the thermoplastic polymer, the tackifier, and the wax has at least one carboxylic anhydride group or carboxyl group. (c) A phosphoric acid ester represented by general formulas (1) to (3) is an addition reaction product of monoepoxyphenol, monoepoxyalkylphenol or aliphatic monoepoxide with phosphoric acid, phytic acid or phosphorous acid. One or a mixture of two or more selected from the group, and either a thermoplastic polymer, a tackifier, or a wax,
At least one carboxylic anhydride group or carboxyl group
The hot melt adhesive composition according to (a) above, characterized in that the hot melt adhesive composition has the following properties: (d) Phosphoric esters represented by general formulas (1) to (3) are combined with benzylphenol, α-methylbenzylphenol or their alkylene oxide adducts, and phosphorus pentoxide, phosphorus trichloride or phosphorus oxychloride. one type or a mixture of two or more selected from the group of addition reaction/hydrolysis products, and either the thermoplastic polymer, the tackifier, or the wax has at least a carboxylic anhydride group or a carboxyl group. The hot melt adhesive composition according to (a) above, characterized in that it has one. (e) The thermoplastic polymer is butyl rubber, styrene-ethylene-butylene-with a molecular weight in the range of 20,000 to 1,500,000.
Styrene resin, styrene-butadiene-styrene resin,
Group of styrene-ethylene-propylene resins, ethylene-propylene resins, ethylene-acrylic ester resins, atactic polypropylene resins, polyacrylic ester resins, polystyrene resins, polyα-methylstyrene resins, polyester urethane resins, polyether urethane resins 5 to 80% by weight of a mixture of two or more selected from
The hot melt adhesive composition according to any one of (a) to (d) above, characterized in that the composition contains 5 to 30% by weight of a tackifier that is a stabilized rosin or a rosin ester derivative thereof. thing. (F) The hot melt adhesive composition according to any one of (A) to (E) above, wherein the wax component contains at least 5% by weight of a crystalline wax having a softening point temperature of 130° C. or higher.

The present invention will be explained in detail below. As described above, the hot melt adhesive composition of the present invention includes the above general formulas (1) to (3) as hot melt adhesive constituents.
This is a hot melt adhesive composition containing 0.1 to 30% by weight of one type or a mixture of two or more types selected from the group of phosphoric acid esters shown below. A hot melt adhesive composition containing a certain amount of phosphoric acid ester represented by the general formulas (1) to (3) has good compatibility, stable melt viscosity characteristics, and excellent oil surface properties. It is possible to demonstrate the wear characteristics. It has also been found that the influence of the internal plasticizer for vinyl chloride resin on the plasticizer migration resistance can be extremely reduced. The active phosphoric acid group of the phosphoric acid ester exhibits the so-called complex formation (chelate formation) effect with the metal, and even the untreated metal surface is thinly coated with substances such as processing oil. The most important feature is that hot melt adhesives have excellent wettability due to their strong affinity for metals, and as a result, they can be bonded instantly without any treatment. Furthermore, in the present invention, the phosphoric acid esters represented by the general formulas (1) to (3) are basically the thermoplastic polymer of the present invention,
It is preferable to select and use substances that are compatible with components such as tackifiers and waxes, but they do not necessarily have to be completely uniformly compatible, but must be compatible with any one component. If so, it can be preferably used. That is, as the phosphoric ester of the present invention, those obtained by the following method are mentioned as typical examples, and those obtained by the above general formulas (1) to (3)
), R is preferably an alkyl group having 1 to 12 carbon atoms, a phenyl group, a diphenyl group, a benzyl group, a benzylphenyl group, an α-methylbenzyl group, or an α-methylbenzylphenyl group rather than hydrogen. Moreover, groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, heptyl, hexyl, decyl, dodecyl, nonyl, and the like. Also,
R' represents an alkylene group having 2 to 4 carbon atoms, and is preferably an ethylene group, a propylene group, a butylene group, or a hydroxypropylene group. Typical examples of general formula (1) include those obtained by directly converting epoxidized phenol, epoxidized alkylphenols, aliphatic monoepoxides, etc. into phosphoric acid esters with phytic acid. Further, as general formula (2), for example, phenol,
Benzylphenol, α-methylbenzylphenol,
Direct phosphoric acid esterification of fatty alcohols with phosphorus pentoxide, phosphorus oxychloride, etc., or phenol,
Benzylphenol, α-methylbenzylphenol,
Suitable examples include those obtained by subjecting an adduct obtained by addition-reacting an alkylene oxide to each fatty alcohol and subjecting it to a phosphoric acid esterification reaction with phosphorus pentoxide or phosphorus oxychloride in the same manner as described above. Among the above, the number of moles of alkylene oxide added is preferably 0 to 20 moles, especially with respect to phenol or fatty alcohol, and if it is more than this, the compatibility with other constituent components of the hot melt adhesive will be extremely poor. There are cases where it becomes defective, which is not desirable. Also, the general formula (3
), suitable examples include those obtained by directly reacting epoxidized phenol, epoxidized alkylphenols, and aliphatic monoepoxides with phosphorous acid.

[0008] The amount of phosphoric ester blended in the present invention is 0.1
~30% by weight is suitable. The amount of phosphate ester blended is
If the amount is less than 0.1%, oil surface adhesion properties will not be exhibited at all, and if it is used in excess of 30%, problems will arise in terms of rigidity, heat resistance, and cost of the hot melt adhesive composition. Preferably 1 to 20% by weight, more preferably 1 to 5% by weight
It is best to use within the range of weight %.

Examples of thermoplastic polymers that can be preferably used as the thermoplastic polymer of the present invention include thermoplastic polymers whose number average molecular weight determined by high performance liquid chromatography is in the range of 20,000 to 1,500,000, preferably in the range of 20,000 to 500,000. Plastic polymers are preferred, and thermoplastic polymers that are compatible with the tackifier and wax component used in the present invention can be used more preferably, and the following are representative ones [trade names are in parentheses] Same below] Butyl rubber [Japan Butyl 065, 365,
AID chlorobutyl 1066, etc.], partially cross-linked butyl rubber [Polycer XL-20, etc.], polyisobutylene resin [Exxon-Vistanex L-80, Exxon L-120, etc.],
Styrene-ethylene-butylene resin, styrene-ethylene-butylene-styrene block copolymer [Clayton G-1657, Clayton GX-1726, Clayton G-1652,
Styrene-ethylene-propylene block copolymer [Kraton GX-1701, etc.] , styrene-isoprene-styrene block copolymer [Califlex T
R-1107, TR-1111, TR-1117,
JSR SIS-5000 etc.], styrene-butadiene-styrene copolymer [Califlex TR-110
2, JSR TR-1101, JSR TR-2000, Asaprene T-431, T-414, etc.], ethylene-propylene resin [JSR EP-11, JSR EP-07,
EP-02, etc.], polyacrylic acid ester resin [Ni
pol AR-51, etc.], polyester elastomer resins [DuPont Hytrel, etc.], modified polyethylene (
Melt index value at 180℃ 5-200g/1
0 minutes), ionomer resin [Himilan resin etc.], ethylene-vinyl acetate copolymer [Evaflex resin], ethylene-acrylic acid ester copolymer (acrylic acid ester content 1-45%, melt index value at 180°C) 0.1 to 750g/10 minutes), atactic polypropylene, polystyrene resin, polyα-methylstyrene resin, polyester resin, polyamide resin, polycarbonate resin, polyimide resin, polyester urethane resin, polyether urethane resin, polyester ether urethane It is common to use 5 to 80% by weight, particularly preferably 5 to 45% by weight, of one or more types of thermoplastic polymers such as resins, and use at most 5 or less types. If it is less than 5% by weight, the heat resistance strength tends to be lacking, and if it is more than 80% by weight, the viscosity of the hot melt adhesive increases, resulting in a marked decrease in coating workability and the wetting of the material to be bonded. It tends to have poor characteristics. Particularly preferred are butyl rubber, styrene-ethylene-butylene-styrene resin, styrene-ethylene-butylene resin, styrene-ethylene-propylene-styrene resin, ethylene-propylene resin, ethylene-acrylate resin, atactic polypropylene,
Polyacrylic ester resin, polystyrene resin, polyα-methylstyrene resin, polyester urethane resin,
One or more selected resins selected from the group of polyether urethane resins, polyether urethane resins, and polyester ether urethane resins. The hot melt adhesive composition according to the present invention can provide a hot melt adhesive composition having both appropriate rigidity and toughness. In other words, it is preferable to select and use resins that can exhibit the characteristics of both toughness and rigidity, such as a combination of styrene block copolymer resin and rubber resin, or a combination of crystalline resin and rubber resin. preferable. However, if attention is paid to low-temperature adhesion properties, this is not the only option.

Further, in the present invention, it is more preferable that the thermoplastic polymer is an acid-modified thermoplastic polymer in which at least one carboxylic anhydride group or carboxyl group is introduced into the molecule in advance. Further, in the present invention, a tackifier is used for the following reasons. That is, the hot melt adhesive composition of the present invention is highly effective in reducing the viscosity, adjusting wetting characteristics (improving workability), adjusting hot tack force, adjusting open time, etc., and exhibits favorable instant adhesive properties. This is because it is important for There are no particular restrictions on the tackifier used in the present invention, and any known tackifier may be used. For example, the following are typical [product names in parentheses are the same]. (Hydrogenated) aromatic or aliphatic petroleum resins [Alcon P or M series, Quinton A series, etc.],
Terpene resin [Piccorite series, YS resin TO series, Clearon P or M series, etc.]
, terpene-phenol copolymer resin [YS Polyster T
series, 2000 series, etc.], polymerized or stabilized rosin or transparent rosin, as well as their rosin ester derivatives or their hydrogen adducts, hydrogenated dicyclopentadiene resins [Escolettes 5300, etc.], low-molecular styrene resins, In addition to coumaron-indene resin, ketone resin, xylene resin, etc., C5 petroleum resin obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, and 1,3-pentadiene produced by thermal decomposition of petroleum naphtha. , C9-based petroleum resin obtained by copolymerizing C9 fractions such as indene, vinyltoluene, α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha, and copolymerized petroleum oil of the C5 fraction and C9 fraction. Representative examples include resins and the like. Further, in the present invention, it is more preferable that the tackifier is a modified tackifier in which at least one carboxylic anhydride group or carboxyl group is introduced into the molecule in advance. In particular, stabilized rosin or its rosin ester derivative resin is highly preferred because it already has a considerable amount of carboxyl groups in its molecules, is easily available, and has a high effect on adhesion. Although there are no particular restrictions, the tackifier may include:
They are used alone or in combinations of 1 to 60% by weight, preferably 5 to 30% by weight.

Further, in the present invention, wax is used for the following reasons. In other words, the use of wax has high effects such as lowering viscosity, adjusting wetting characteristics (improving workability), preventing blocking, adjusting open time, and improving heat resistance, and exhibits favorable instant adhesive properties. This is because it becomes possible. That is, although there are no particular restrictions on the wax used in the present invention, the following waxes can be preferably used. Polyethylene wax [Neowax series,
High wax series], polypropylene wax [
Viscole series], paraffin wax, microcrystalline wax, natural wax, etc. are preferred. Further, in the present invention, it is more preferable that the wax is modified so that at least one carboxylic anhydride group or carboxyl group is introduced into the molecule in advance. Although there are no particular restrictions, the above-mentioned waxes may be used singly or in combination in an amount of 50% by weight or less, preferably 30% by weight or less, and more preferably 1 to 20% by weight. If the wax content is 50% by weight or more, the open time becomes too short and adhesive workability tends to be poor, and low-temperature adhesive properties etc. become a problem, so it is difficult to say that it is common. Among the wax components, it is preferable to select and use a crystalline wax with a softening point temperature of 100° C. or higher, preferably 130° C. or higher. Among them, the use of at least 5% by weight of high-density polyethylene wax or polypropylene wax allows the hot melt adhesive composition of the present invention to be prepared with high heat resistance and to have an appropriate crystallization rate or solidification rate. It is highly preferred because it provides excellent wetting properties for metals.

In the present invention, an acid-modified thermoplastic polymer, an acid-modified adhesive, in which at least one carboxylic anhydride group or carboxyl group (hereinafter simply referred to as an [anhydrous) carboxyl group] has been previously introduced into the molecule. The imparting agent is preferably acid-modified wax. The main reason for this is that, first, when adhering to poor quality vinyl chloride, the transferability of the plasticizer internally added to poor quality vinyl chloride is significantly reduced. Second, it improves wettability to metal surfaces. The third reason is that the adhesive durability after oil surface adhesion increases. The (anhydrous) carboxyl group-introduced resin includes those obtained by the methods shown below and the following resins that are conventionally easily available on the market. Products that are easily available on the market include, for example, acid-modified thermoplastic polymers such as maleic anhydride graft-modified styrene-ethylene-butylene-styrene block copolymers, acid-modified polypropylene wax, acid-modified polyethylene wax, and acid-modified paraffin. There are acid-modified waxes such as wax. Grafting is the most common method for introducing (anhydrous) carboxyl groups, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, citraconic acid, It can be obtained by grafting citraconic anhydride, acrylic acid, methacrylic acid, etc., respectively. In addition, the hot melt adhesive composition of the present invention may further contain the following plasticizers, pigments, fillers, ultraviolet absorbers or ultraviolet stabilizers, antioxidants or antiaging agents, and other silane-based There is no problem in using a coupling agent, a titanate coupling agent, a gel preparation agent, etc. as appropriate and necessary, and the substances shown below are representative and can be preferably used. The use of plasticizers can impart appropriate rubber elasticity, and there is no problem in using them for the purpose of improving low-temperature adhesive properties. For example, liquid polybutene, molecular weight 5000
-12,000 low molecular weight polyisobutylene [trade name Vistanex etc.], paraffin oil, naphthenic oil, process oil, linear fatty acid ester, etc. One or two or more types selected from the group such as Mixtures are suitable.

[0013] As fillers, fillers having a particle size of 100 mesh or less, such as carbon black, talc, clay, silica, barium sulfate, calcium carbonate, barium carbonate, magnesium oxide, and titanium oxide, are commonly used in paints and adhesives. Fillers may also be used. As the ultraviolet absorber, for example, existing chemical substance No. (5)-544
, No. (5) 5459, No. (5)-3580,N
o. (5)-545, No. (5)-3605, No.
(5) Benzotriazole compounds such as -3604,
Existing chemical substance no. (3)-2830, No (3)-2
Oxazolic acid amide compounds such as 800,
Existing chemical substance no. Examples include benzophenone compounds such as (4)-141, preferably 0.1 to 3% by weight.
used. Examples of UV stabilizers include hindered amine-based existing chemical substance No. (5)-3732,N
o. (5)-5501, No. (7)-2132, No.
．． (5)-5457 or the like may be used in an amount of 0.05 to 3% by weight. Examples of antioxidants include existing chemical substance No. (5)-1079, No. (3)-1693,N
o. (3)-3094, No. (3)-1737, No.
．． (3)-1120, No. (3) Hindered phenol compounds such as -2086, existing chemical substance No. (3
)-3510, No. (3)-2530, NO. (3)
-2501, NO. A phosphoric acid ester compound such as (2)-1894 may be used in an amount of 0.1 to 2% by weight.

The hot melt adhesive composition of the present invention generally has a melt viscosity at 200°C of 200,000 centipoise or less, preferably 500 centipoise to 50,000 centipoise, from the viewpoint of coating workability. preferable. When applying to a rough adherend, it is preferable that the hot melt has a low melt viscosity. That is, since the viscosity behavior of a hot melt adhesive affects its wetting properties, it is also important to design the viscosity and thixotropic properties to suit the surface condition of the adhesive. The hot melt adhesive composition of the present invention may be produced by any known production method. For example, each component may be mixed and melted under heating in a nitrogen stream, if necessary, using a powerful stirring and mixing device such as a general vertical reactor or a Banbury type kneader, and there is no particular restriction. Generally, 120℃~2
It may be obtained by heating it at a temperature in the range of 00° C. for several hours until it becomes completely molten, and there are no particular restrictions. Further, the form of the product of the hot melt adhesive composition of the present invention is not particularly limited, and examples include tape, pellet, etc.
block, film, stick, powder,
It may be handled in any form such as filled in cans. Furthermore, there are no particular restrictions on the application method or adhesion/sealing method of the hot melt adhesive composition of the present invention, and there are no particular restrictions on the application method or adhesion/seal processing method, and application methods such as bead-like application, planar application, dot-like application, etc. using a known hot melt applicator or hand gun. It may be handled using conventional adhesive processing methods such as pressure bonding using a heat roll or cooling roll, pressure bonding using a special jig, press bonding, high frequency reheating bonding, and ultrasonic heat bonding.

[0015]

[Examples] In order to explain the present invention more specifically, Examples and Comparative Examples will be given below, but the present invention is not limited to these Examples. In addition, the ratio of each component in Examples is expressed as parts by weight, and the effects of the present invention are described. Further, the metal surface-treated steel sheet used in the oil surface adhesion test described in the examples was prepared as follows. Thickness 0.5mm, 1
An inch-wide SPCC steel plate was soaked in press oil and held vertically for 1
After being left for 0 minutes, the test piece was further soaked in anti-rust lubricating oil and excess oil was removed using an air spray gun, and the same size industrial SPCC steel plate obtained from Nippon Test Panel Co., Ltd. and treated with anti-rust oil was used. It was used as an adhesion test piece. For hot-dip galvanized steel sheets, we used test pieces obtained by immersing them in an aqueous emulsion-type lubricating oil containing natural vegetable oil, mineral oil, glycol derivatives, etc. as the main ingredients, taking them out, and draining them with an air spray gun. In addition, in the rust prevention durability test of adhesive durability using the hot melt adhesive composition described in the practical example, it was applied to a steel plate to a thickness of about 20 to 30 microns, and after being left for one week, it was applied with a sharp cutter knife. Cross-cuts are made on the coating surface to reach the metal surface, and then immersed in city water at 40°C so that half of the specimen is exposed to the air, left for 3 to 5 days, and then taken out to examine the rust on the metal and the coating. Changes in membrane adhesion were observed. In addition, in the heat stability test of the hot melt adhesive composition described in the practical examples, 100 gr of melt was placed in a 200 ml glass beaker, heated in a heating dryer for a certain period of time, and then taken out. observed.

Example 1 46 parts of a 60% phytic acid aqueous solution was reacted with 30 parts of monoepoxyphenol (another name: phenyl glycidyl ether) under conditions of 70 to 80°C for 1 hour, and then dehydrated in a vacuum dryer at 30°C. As a result, a phytic acid ester compound (1) having an average addition of 4 moles was obtained. Separately, 14.2 parts of phosphorus pentoxide was added to 146 parts of a 10 molar equivalent adduct of ethylene oxide to 1 molar equivalent of nonylphenol in a nitrogen stream at 70 to 80°C for 45 minutes. The mixture was aged for 3 hours to obtain a phosphoric acid ester compound (2). Copolymerized with 5 parts of phytic acid ester compound (1) or 5 parts of phosphoric acid ester compound (2) and ethylene-ethyl acrylate resin (hereinafter referred to as EEA) under the trade name Evaflex EEA A-703 (25% ethyl acrylate). , Mitsui DuPont Polychemical Company products)
and 10 parts of Kraton G-1652 (trade name, containing 29% styrene, Shell Chemicals) as a styrene-ethylene-butylene-styrene block copolymer resin (hereinafter referred to as SEBS), hydrogenated with a softening point temperature of 105°C. Dicyclopentadiene resin: 22.5 parts of the trade name Escolettes 5300 (Tonex product), 10 parts of the trade name Super Ester A-115 (Arakawa Chemical Products) as a rosin ester derivative, acid-modified polypropylene wax (hereinafter referred to as PP)
Product name: Viscole TS-2 (abbreviated as wax)
10 parts of 00 (Sanyo Chemical Industries product), 5 parts of naphthenic oil as a plasticizer, 0.25 parts of trade name Irganox 1010 (Ciba Geigy product) as a hindered phenol anti-aging agent, trade name Tinuvin as an ultraviolet absorber. - 0.25 parts of P (Ciba Geigy products) completely
Mixing and melting was carried out at a melting temperature of 70°C. Hot melt adhesive compositions [hereinafter simply referred to as melts] (Melt-A) and (Melt-B) were obtained in the order of phosphoric acid ester description. The melt viscosity at 190° C. of the obtained Melt-A and Melt-B was about 20,000 centipoise. Further, the viscosity changes after the thermal stability test at 190° C. for 48 hours were both stable within 10%, and no abnormalities such as stiffness were observed.

Example 2 16 parts of phosphorous acid was added to 30 parts of monoepoxyphenol (also known as phenyl glycidyl ether) at 70 to 80°C.
The phosphite compound (
3) was obtained. Separately, 14.2 parts of phosphorus pentoxide was added to 80 parts of an adduct of 10 molar equivalents of ethylene oxide per 1 molar equivalent of benzylphenol in a nitrogen stream at 70 to 80°C for 45 minutes, and a reaction was carried out. After aging for a time, 1 part of water was further added to obtain a phosphoric acid ester compound (4). A hot melt adhesive composition (Melt-C) was obtained by completely mixing and melting 2 parts of phosphoric acid ester compound (3), 8 parts of phosphoric acid ester compound (4), and the following components at a melting temperature of 160°C. Ta. As EEA resin, 20 parts of the product name Evaflex A-701 and 10 parts of the same A-709 S
As EBS resin, the product name is Tuftec H-1052 (20
% styrene (containing Asahi Kasei products), 30 parts of hydrogenated C5-C9 resin with a softening point temperature of 115°C as a tackifier: trade name Admarve P-115 (Idemitsu Petrochemical Products),
Product name: Viscoll TS-20 as acid-modified PP wax
14.5 parts of Irganox 1010 (a Ciba Geigy product), 0.25 parts of Tinuvin-P (a Ciba Geigy product), 180°C melt viscosity of the obtained Melt-C and 180 A comparison of the viscosity change after the thermal stability test after 48 hours at °C showed that the change rate was stable within 10% and no abnormalities such as stiffness were observed.

Example 3 36 parts of phosphorus pentoxide was added to 134 parts of 2 molar equivalent adduct of butylphenol with propylene oxide at 70-80°C.
The phosphoric acid ester compound (5
) was obtained. Phosphate compound (4) obtained in Example 2
or 15 parts of phosphoric acid ester compound (5) and the following components were completely mixed and melted at a melting temperature of 160°C to prepare hot melt adhesive compositions (melt-D) and (melt -E) was obtained. Butyl rubber: 15 parts of trade name JSR Butyl 365 (product of Nippon Gosei Rubber Co., Ltd.) Maleic anhydride graft-modified SEBS resin: 20 parts of trade name Kraton G-1901X As tackifier: 20 parts of atactic polypropylene Transparent rosin ester resin: 20 parts of trade name KE-311 (Arakawa Chemical Products) 10 parts of trade name Hiwax 410P (Japan Petrochemical Products, softening point temperature 122°C) as polyethylene wax (hereinafter abbreviated as PE wax) Irganox 0.3 part of 1076 (Ciba Geigy product) 0.25 part of Tinuvin-P (Ciba Geigy product) Carbon black 0.02 part Colloidal silica (Aerosil #200) 1.0 part Rutile type titanium white 25 parts Obtained melt The melt viscosity at 190° C. of Melt-D was approximately 4.5 to 50,000 centipoise. Also 19
The viscosity change after the thermal stability test at 0° C. for 48 hours was stable within 10%, and no abnormalities such as stiffness were observed.

Example 4 250 parts of a double-hydroxylated oligoester with a number average molecular weight of 2,500 prepared from a 1:1 mixed diol of 1,6-hexanediol and 1,5-pentanediol and phthalic anhydride. 50 parts of polyester urethane resin obtained by reacting 23.5 parts of tetramethylxylylene diisocyanate with 2 of Kraton GX-1701 as a styrene-ethylene-propylene block copolymer.
0 parts and the phosphoric acid ester compound (1) obtained in Example 1
2.5 parts of rosin ester derivative (trade name Super Ester A-100) and 25 parts of rosin ester derivative (trade name Super Ester A-100) and trade name Hiwax 2
A hot melt adhesive composition (Melt-F) was obtained from 5 parts of 203A (acid-modified PE wax, Mitsui Petrochemical Products).

Comparative Example 1 35 parts of Evaflex EEA A-703 (25% copolymerized as ethyl acrylate, product of Mitsui DuPont Polychemicals) and the following thermoplastic polymers, tackifiers, waxes, and plasticizers. , various additives were added and blended to form the hot melt adhesive composition (Melt-1) listed in Table-1.
I got it. Product name: Clayton G-16 as SEBS
10 parts of Hydrogenated dicyclopentadiene resin with a softening point temperature of 105°C:
Product name Escolettes 5300 (Tonex product) 45
Product name: Super Ester A as a rosin ester derivative
10 parts of -115 (Arakawa Chemical Products) 10 parts of the trade name Viscol TS-200 as a PP wax (product of Sanyo Chemical Industries) 5 parts of naphthenic oil as a plasticizer 0.25 parts of the trade name Irganox 1010 as an anti-aging agent
(Ciba Geigy products) 0.25 parts of the trade name Tinuvin-P as an ultraviolet absorber (Ciba Geigy products)

[
Comparative Example 2 Product name of Comparative Example 1: Evaflex EEA A-7
Instead of 03, ethylene-vinyl acetate resin (hereinafter EVA
Except that it was a 1:1 mixture of Evaflex #250 (vinyl acetate content 28%) and Evaflex #450 (vinyl acetate content 19%) under the trade name
A similar hot melt adhesive composition (Melt-2) was prepared.

Comparative Example 3 Product name of Comparative Example 1: Evaflex EEA A-7
Product name: Califlex TR- as SIS instead of 03
1107 (14% styrene content) and Cauliflex T
A similar hot melt adhesive composition (Melt-3) was prepared except that it was a 1:1 mixture of R-1111 (21% styrene content).

Comparative Example 4 Product name: Evaflex EEA A described in Comparative Example 1
-703 as butyl rubber: 10% of the trade name JSR Butyl #365 and polyisobutylene: 10% of the trade name Vistanex L-80 (Exxon product) and 80% of weight average molecular weight Atictec polypropylene with a softening point temperature of 140°C A similar hot melt adhesive composition (Melt-4) was prepared except that a mixture of the following was used.

[0024] All adhesive test pieces were prepared in the following manner. Using a handgun that melts the test melt at a melting temperature of 180° to 200°C, the test melt was applied to one side of the metal, and the other test piece was immediately placed and pressed for 2 to 10 seconds to complete the adhesion. . Adhesive thickness is 150 microns ~
Adjusted between 350 microns. In the case of melts (melts A, B, 1, 2) with relatively short open times of less than 10 seconds because they were glued by hand, the metal material for testing should be preheated to about 50 to 60°C. Adhesion was carried out using Even when bonding without preheating, the open time is 2~
Approximately 75% of the measured values listed in Table 1 when carried out in 3 seconds
The above strength retention rate was shown even at the lowest value, and an improvement in adhesive strength was observed in the cases of Melt-A and B over time. Therefore, preheating is optional and does not particularly limit the present invention.

[0025]

[Table 1]

[0026]

[Table 2]

<Symbol explanation> Conditions for *-1: Product immersed in press oil/antirust oil (details described above) Conditions *-2: Product immersed in mineral oil-based emulsion-type lubricating oil (details immersed in press oil/antirust oil) method)*-3 Conditions: Vegetable oil (coconut oil)-based emulsion-type lubricating oil immersion treated product (method described above in detail)*-4 conditions: Kure Kogyo product rust preventive oil (5-56)
After being left for one day after spray coating, it was wiped gently with a cloth. *-5 condition: Nippon Test Panel Co., Ltd. commercially available test specimen (
Oil surface treated product). PP: Polypropylene 25mm width x 75mm length, 5m
m thickness plate VC: Soft vinyl chloride 25mm width x 75mm length, 5m
m-thick plate shear stage strength retention rate (%): (Shear stage measured value after environmental test ÷ initial value shear stage adhesive strength) x 100 [value measured at 20°C]. Impossible: Indicates a state in which the material has peeled off before being subjected to measurement. Boundary failure: When the peeling state is complete metal interface peeling. Corrosion test results ◎: Corrosion (rust) is only visible on exposed metal parts and almost no protected paint film is visible. ○: Corrosion (rust) is within about 1 mm around the cross cut, and no blistering or peeling is observed on the other coating surfaces. △: When corrosion (rust) is observed not only on exposed metal parts but also within about 5 mm around the cross-cut, or when corrosion (rust) is observed with partial peeling and peeling of the paint film. ×: When the paint film is completely peeled off or is corroded (rust)
This occurs not only on exposed metal parts but also on all surfaces where the paint film has peeled off.

[0028]

Effects of the Invention From the Examples, as is clear from the Comparative Examples, with the conventional hot melt adhesive compositions, the adhesion is extremely small or incomplete, and the T-peel strength is particularly low, and all metal interface peeling occurs. presented. The phenomenon of metal interface delamination and low adhesive strength is due to the fact that the oil present on the metal surface affects the wettability to the metal, the chemical bond with the metal, etc., which are necessary properties for adhesion. It is reasonable to judge that it is inhibiting the oil content, which indicates that the influence of oil content is extremely large. In addition, in the comparative example, the strength decreased significantly even after the environmental test, and it was estimated from the measured values that the practicality was substantially poor. On the other hand, it is clear that the hot melt adhesive composition of the present invention exhibits excellent adhesion to oil surfaces, and the strength after the environmental test was actually improved, and adhesion was promoted by heat curing. Got the results. The rust prevention effect was also found to be high, as rust was rarely observed in areas other than exposed metal parts when immersed in hot water or salt water. It has been confirmed that the hot melt adhesive composition of the present invention described in the examples is a melt that exhibits an open time of approximately 15 seconds to 1 minute, and that adhesion is completed within 15 seconds at the longest set time. High workability and productivity were confirmed. In other words, the effect of the present invention is that while taking advantage of the characteristics of hot melt adhesives such as instant adhesion, non-pollution, and long-term thermal stability, oil surface metal adhesion is developed as a property that has been difficult to obtain until now. In addition, it has been found that sufficient adhesion to hard-to-adhesive plastics and rust prevention to metals can be obtained. The manifestation of these effects is presumed to be due to the strong affinity, chemical reactivity, and bond stability of the ()phosphorous acid group or phosphoric acid group to the metal surface, and the new affinity of the oil on the metal surface to the metal ( It is presumed that adhesion is achieved by incorporating oil into the hot-melt adhesive composition, as it shows a much higher affinity than the hot-melt adhesive composition (SP value). In addition, it has been found that the hot melt adhesive composition of the present invention has excellent heating stability and non-polluting properties, which are important in terms of applicator properties. The above-mentioned properties indicate that conventionally known hot-melt adhesive compositions do not exhibit satisfactory adhesion in an adhesion test on oily metal materials, and the adhesion is extremely incomplete, resulting in deterioration over time. As a result, it was observed that the metal corroded and the bond was destroyed. Therefore, the hot-melt adhesive composition of the present invention provides a novel, highly reliable hot-melt adhesive composition that is optimal for adhesion and sealing between metals and dissimilar materials. It can be preferably used not only for adhesion between plastics and metals, but also for lamination between various plastics and metals, adhesive/sealing applications, metal protective coatings, anti-slip applications on metal surfaces, and adhesion of dissimilar materials other than metals and plastics.

Claims (6)

[Claims] Claim 1: A hot melt adhesive comprising a thermoplastic polymer, a tackifier and/or a wax,
and one or more selected from the group of phosphoric esters represented by the following general formulas (1) to (3), in an amount of 0.1 to 3
A hot melt adhesive composition characterized by containing 0% by weight. [R-O-(R'O)m]a-X (1) [R-O-
(R'O)m]b-Y (2) [R-O-(R'O)
m]c-Z (3) (wherein, R has 1 to 1 carbon atoms
2 alkyl group, phenyl group, diphenyl group, benzyl group, benzylphenyl group, α-methylbenzyl group, α-
Methylbenzylphenyl group, R' represents an alkylene group having 2 to 4 carbon atoms or a hydroxypropylene group, m is 0
-20, a is an integer of 1 to 6, b and c are integers of 1 to 2, X is a phytic acid group, Y is a phosphoric acid group, and Z is a phosphorous acid group. ) [Claim 2] Thermoplastic polymer,
2. The hot melt adhesive composition according to claim 1, wherein either the tackifier or the wax has at least one carboxylic anhydride group or carboxyl group. 3. The phosphoric acid ester represented by the general formulas (1) to (3) is combined with monoepoxyphenol, monoepoxyalkylphenol or aliphatic monoepoxide,
One type or a mixture of two or more types selected from the group of addition reaction products with phosphoric acid, phytic acid, or phosphorous acid, and either the thermoplastic polymer, the tackifier, or the wax is anhydrous. The hot melt adhesive composition according to claim 1, which has at least one carboxylic acid group or carboxyl group. Claim 4: The phosphoric acid ester represented by the general formulas (1) to (3) is composed of benzylphenol, α-methylbenzylphenol, or an adduct of an alkylene oxide thereof, and phosphorus pentoxide, phosphorus trichloride, or oxychloride. One type or a mixture of two or more types selected from the group of addition reaction/hydrolysis products with phosphorus, and either the thermoplastic polymer, the tackifier, or the wax has a carboxylic anhydride group or a carboxyl group. The hot melt adhesive composition according to claim 1, characterized in that it has at least one. [Claim 5] The thermoplastic polymer has a molecular weight of 2 to 15.
Butyl rubber, styrene-ethylene-butylene-styrene resin, styrene-butadiene-styrene resin, styrene-ethylene-propylene resin, ethylene-propylene resin, ethylene-acrylic acid ester resin, atactic polypropylene resin, polyacrylic 5 to 80% of a mixture of two or more selected from the group of acid ester resin, polystyrene resin, polyα-methylstyrene resin, polyester urethane resin, and polyether urethane resin.
5. The hot melt adhesive composition according to claim 1, further comprising 5 to 30% by weight of a tackifier which is a stabilized rosin or a rosin ester derivative thereof. . [Claim 6] The wax component has a softening point temperature of 130°C.
The hot melt adhesive composition according to any one of claims 1 to 5, characterized in that it contains at least 5% by weight of the above crystalline wax.