JPS5840587B2 - hot melt resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable hot melt resin composition.

The hot melt resin composition contains an ethylene/vinyl acetate copolymer (E/■A), polyethylene, polyvinyl acetate, and polyamide as a base polymer, a rosin resin, a petroleum resin, and a viscosity reducing agent during melting as a tackifying component. It consists of waxes and the like, and is used in a wide range of fields such as bookbinding, packaging, and construction work.

This hot melt resin composition is solvent-free and cures quickly, so it is widely used in fields such as coatings, inks, and adhesives. Due to the use of resins, petroleum resins, etc., and its curing mechanism, its use in fields where hot water resistance, heat resistance, solvent resistance, etc. are required has been restricted.

As a result of intensive research, the present inventors solved the defects of these conventional hot melt resin compositions, and after curing,
This led to the invention of a hot melt resin composition that exhibits excellent solvent resistance, heat resistance, and hot water resistance.

That is, the present invention uses 30 to 70 parts by weight of the base polymer,
Rosin resin having a polymerizable unsaturated double bond 1 obtained by reacting a rosin resin having a functional group with a compound having a functional group bonding to the functional group and a polymerizable unsaturated double bond
20 to 50 parts by weight of a tackifier, including 0 to 50 parts by weight;
A hot-melt resin composition further comprising 97,230 to 30 parts by weight and 0 to 30 parts by weight of a polymerizable unsaturated monomer, particularly a rosin resin containing a carboxyl group, a lower alkyl ester thereof, or a hydroxyl group, as required. and a compound having a polymerizable unsaturated double bond and a carboxyl group or a lower alkyl ester thereof or a functional group that reacts with a hydroxyl group. The present invention relates to a hot melt resin composition.

In the present invention, the rosin-based resin having a functional group includes those having a carboxyl group or a lower alkyl ester group such as rosin, abietic acid and their methyl esters, or their water additives, rosin or abietic acid, or those having a carboxyl group or a lower alkyl ester group thereof, Water additives with hydroxyl groups such as polyhydric alcohol esters such as ethylene glycol, chrycerin, diethylene glycol, and pentaerythritol, those with carboxyl groups such as maleic acid-modified and fumaric acid-modified rosins, and maleic acid resins. Examples include those having a carboxyl group and a hydroxyl group, and those having an isocyanate group or an epoxy group obtained by adding polyisocyanate or polyepoxide to the above-mentioned functional groups.

Compounds that have a functional group and a polymerizable unsaturated double bond for chemically bonding with the functional group of the rosin resin as mentioned above include allyl alcohol and cinnamyl alcohol.
(O-hydroxystyrene) m-hydroxystyrene (3-methoxy-4-hydroxystyrene, hydroxyethyl methacrylate, propylene glycol monoacrylate, etc.) Hydroxyl group-containing monomers (e.g., vinyl ethylene oxide, glycidyl methacrylate, etc.) epoxy group-containing monomers (vinyl phenyl isocyanate) Isocyanate group-containing monomers such as t, vinyl isocyanate, impropenyl incyanate, amide groups such as acrylamide, O-aminostyrene, vinylbenzylamine, ethanolamine vinyl ether, allylamine, 1-vinyl-1-alkylguanisidine, etc. or amino group-containing monomers, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid,
Alternatively, a carboxyl group-containing rosin resin is reacted with an epoxy group such as gepoxide, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, etc. to form a double bond with the remaining epoxy group.
A monomer having a functional group such as a carboxyl group or an amino group is reacted, or a carboxyl group-containing rosin resin is reacted with a diisocyanate compound or a polyisocyanate compound such as 2,4-toluene diisocyanate,
It can be introduced by a method such as reacting the isocyanate with inocyanate such as xylene diisocyanate, and reacting the remaining isocyanate with a heptamer having a functional group such as a carboxyl group or an acid group and further having a double bond.

The reaction between a functional group-containing rosin resin and a compound that has a functional group that chemically bonds with the functional group and a polymerizable unsaturated double bond should be carried out in a manner that prevents the polymerizable unsaturated double bond from being cleaved or polymerized. Do it with conditions.

That is, a polymerizable unsaturated double bond is introduced into the rosin resin by performing esterification or other reactions in the presence of a thermal polymerization inhibitor.

Specifically, the hot melt resin composition of the present invention has an E/V
A, 30 to 70 parts (by weight, the same applies hereinafter) of a base polymer such as polyethylene, polyvinyl acetate, polyamide, etc., and other rosins containing 10 to 50 parts of the above polymerizable unsaturated double bond-containing rosin resin It consists of 20 to 50 parts of a tackifying agent such as a petroleum resin or a petroleum resin, O to 30 parts of a wax, and O to 30 parts of a polymerizable unsaturated monomer.

It has already been invented as a wax (patent application 1972-1)
38695, Japanese Patent Publication No. 57-42095), a modified wax may be used in which a polymerizable unsaturated double bond is introduced into the carboxyl group of an oxidized wax as in the present invention, or a polymerizable unsaturated monomer may be used. is also effective for increasing the curability, which is the objective of the present invention (Japanese Patent Application No. 51-466)
No. 32.

(Japanese Patent Application Laid-open No. 129750/1983).

After coating or printing, the hot melt resin composition of the present invention undergoes crosslinking due to the cleavage of double bonds when irradiated with ultraviolet rays, electron beams, radiation, etc., or when energy such as heating is applied, resulting in hot melt resistance, heat resistance, and solvent resistance. improvement was obtained.

A sensitizer is used when ultraviolet rays are used as energy to cause crosslinking by cleavage of double bonds, and the ratio of rosin resin with polymerizable unsaturated double bonds/sensitizer is 9.
9.910.1 to 80/20 (weight), preferably 95
It is about 15 (weight).

Sensitizers include benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, α
- Benzoin sensitizers such as methylbenzoin, α-arylbenzoin, α-chlorodeoxybenzoin, ketone sensitizers such as benzophenone and acetophenone, azo sensitizers such as azobisisobutyronitrile, anthraquinone, phenanthrene Examples include quinone sensitizers such as, sulfide sensitizers such as benzyl disulfide, and tetramethylthiuram monosulfide.

In addition, crosslinking occurred due to the cleavage of double bonds by heat, resulting in improvements in solvent resistance, heat resistance, and hot water resistance.

The ratio of the rosin resin thermal polymerization catalyst into which polymerizable unsaturated double bonds are introduced is 99.9510.05 to 99.9510.05.
99/1 (weight), preferably about 99.510.5 (weight).

As the thermal polymerization catalyst, one with a decomposition temperature of 130°C or higher is selected, for example, 2,5-dimethyl-2,5
- Peroxides such as di(t-butylperoxy)hexyne (3), P-menthane hydroperoxide, 2,5-dimethylhexane-2,5-cybidrobar oxide, azobisisobutyronitrile, etc. Azo-based catalysts and the like are used.

Current hot melt coating equipment continues heating (approximately 100°C) for a long time, so the thermosetting type has the disadvantage of crosslinking over a long period of time and short pot life, so it is preferable to use the UV curing type. .

Examples are shown below.

Example 1 200 parts of rosin-based resin steverite resin manufactured by Arakawa Forestry Chemical Industry Co., Ltd. was charged into a four-bottle glass flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a dropping tube, a condenser, and a water trap, and the melting point was further adjusted. After adding 100 parts of microcrystalline wax at about 110℃
The mixture was kept at ℃ and stirred.

Next, 80 parts of glycidyl methacrylate, 0.5 part of hydroquinone, and 0.5 part of pyridine are added dropwise over 1 hour.

The reaction is completed 8 hours after the completion of the dropwise addition. The reaction is terminated when unreacted glycidyl methacrylate is no longer detected by gel permeation chromatography.

50 parts of this mixture of glycidyl methacrylate modified rosin and wax, vinyl acetate content 14 stacked plates, MI value 1
50 parts of E/VA of No. 5 and 1 part of benzophenone were melted and mixed at 160°C, coated on paper, irradiated with ultraviolet rays, and then heated at 140°C, 2
, 5, and heat sealed with the plywood board for 15 seconds.

When this was immersed in boiling water at 100° C. for 2 hours, those exposed to ultraviolet rays did not float or peel at all, but those that were not exposed to ultraviolet rays completely peeled off.

Furthermore, the material that was irradiated with ultraviolet rays only slightly became sticky even in a 120°C oven, but the material that was not irradiated with ultraviolet rays completely melted in an oven at 100°C.

Example 2 Rosin-based resin Rondes R20 manufactured by Arakawa Forestry Chemical Industry Co., Ltd. was placed in a glass 4-hole flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a dropping tube, a condenser, and a water trap.
Add 0 parts and 30 parts of ethylene glycol and heat to 100℃□
A predetermined amount of dehydration was carried out, and 10 hours later, no ethylene glycol was detected by gel permeation chromatography.

Next, 34.8 parts of acrylic acid was added dropwise at 100'C for 1 hour, and 6 hours later, unreacted acrylic acid was no longer detected by gel permeation chromatography, so the reaction was terminated.

30 parts of this monomer-modified rosin, 20 parts of microcrystalline wax with a melting point of about 130°C, vinyl acetate content 14
Weight section, MI value 15 E/VA 50 parts benzophenone 1
The same experiment as in Example 1 was carried out by melt-mixing the two parts, and the same results were obtained.

Example 3 100 parts of rosin-based resin Polyveil Resin manufactured by Arakawa Forestry Chemical Industry Co., Ltd. and 65 parts of glycerin were placed in a glass four-bottle flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a dropping tube, a condenser, and a water trap. When the mixture is kept at 110° C. and stirred, a predetermined amount of dehydration occurs, and after 8 hours, glycerin is no longer detected by gel permeation chromatography.

Next, 33.8 parts of acrylic acid and 0.3 parts of hydroquinone are added dropwise over 1 hour.

Nine hours after the completion of the dropwise addition, unreacted acrylic acid is no longer detected by gel permeation chromatography, and the reaction is complete.

40 parts of this modified rosin, 20 parts of microcrystalline wax with a melting point of about 130°C, a vinyl acetate content of 14 parts by weight,
40 parts of E/VA with an MI value of 15, 1 part of trimethylolpropane triacrylate, and 1 part of benzophenone were melt-mixed and the same experiment as in Example 1 was conducted to obtain the same results.

Example 4 100 parts of rosin-based resin steverite resin manufactured by Arakawa Forestry Chemical Industry Co., Ltd. was charged into a four-hole glass flask equipped with a stirrer, a thermometer, a dropping tube, a nitrogen gas inlet tube, a condenser, and a water trap, and the temperature was heated to 100°C. While keeping the mixture, 45 parts of ethylene glycol diglycidyl ether and 0.3 parts of pyridine were added dropwise, and unreacted ethylene glycol diglycidyl ether was no longer detected by gel permeation chromatography 7 hours after the completion of the dropwise addition.

Next, 19.3 parts of acrylic acid and 0.3 parts of hydroquinone,
0.3 part of pyridine is added dropwise over 50 minutes, and 6 hours after the completion of the dropwise addition, unreacted acrylic acid is no longer detected by gel permeation chromatography, and the reaction is complete.

When the same experiment as in Example 2 was carried out by replacing this modified rosin with the modified rosin of Example 2, similar results were obtained.

Example 5 In a fourth glass flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping tube, and a condenser, 100 parts of rosin-based resin Polyveil Resin manufactured by Arakawa Forestry Chemical Industry Co., Ltd. and a microorganism with a melting point of 110°C were placed. Add 50 parts of Crystalline Wax and 70.3 parts of Hydro+/Stir at 115°C and stir.

Next, 35 parts of acrylamide was added dropwise over 40 minutes, and 8 hours after the completion of the addition, unreacted acrylamide was no longer detected by gel permeation chromatography, and the reaction was complete.

Similar results were obtained when a similar experiment was conducted in which this mixture of modified rosin and wax was used in place of the mixture of modified rosin and wax in Example 1.

Example 6 100 parts of rosin-based resin steverite resin manufactured by Arakawa Forestry Chemical Industry Co., Ltd. is kept at 82° C. and stirred into a glass four-bottle flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping tube, and a condenser.

Next, add 90.5 parts of 2.4-) luene diisocyanate to 4
It was added dropwise for 0 minutes, and unreacted 2,4-toluene diisocyanate was no longer detected by gel permeation chromatography after 10 hours.

Next, 58.2 parts of hydroxyethyl methacrylate and 0.3 parts of hydroquinone are added dropwise over 30 minutes.

Six hours after the completion of the dropwise addition, incyanate was not detected in the infrared absorption spectrum, and the reaction was completed.

When a similar experiment was conducted using this modified rosin in place of the modified rosin of Example 2, similar results were obtained.

Example 7 Mixture of wax and modified rosin of Example 1 60 parts MI value 150 Vinyl acetate content 25 weight φ E/VA 40 parts, P
- 0.5 part of menthane hydroperoxide is heated and mixed at 90°C, coated on an aluminum plate, and then baked in an oven at 160'C for 5 minutes.

This heat-cured coating did not dissolve at all in xylene at 50°C and did not produce any white blisters even after being immersed in hot water at 70°C for 5 hours, but the non-thermocured coating completely dissolved in xylene at 50°C. When immersed in hot water at 70°C for 5 hours, blistering and whitening occurred significantly.

Example 8 In a four-bottle flask equipped with a stirrer, a thermometer, a nitrogen gas inlet pipe, and a condenser, 32 pieces of maleic acid resin waste (manufactured by Arakawa Forestry Chemical Industry Co., Ltd., acid value 140 or lower, ring and ball softening point 130)
400 parts of microcrystalline wax having a melting point of 100°C, and 1 part of hydroquinone were heated and melted at 115°C in a nitrogen gas atmosphere and stirred.

Next, 140 parts of glycidyl methacrylate was added to the dropping tube.
After charging 0.5 parts of pyridine, this was added dropwise over 40 minutes, and the reaction was completed after 9 hours.

The acid value at this time was 0.5. A mixture of 60 parts of this glycidyl methacrylate-modified maleic acid resin and microcrystalline wax and an MI value of 15. 40 parts of E/VA having a vinyl acetate content of 14% by weight and 5 parts of P-menthane hydroperoxide are heated and melted and mixed, coated on a 50 μm thick aluminum foil, and left in an oven at 180° C. for 5 minutes.

After taking them out, they were immersed in ethyl alcohol at 25°C for 5 hours. Those placed in a 180°C oven for 5 minutes showed almost no change, but those that were not placed in the oven were significantly swollen.

Next, MI value 15 vinyl acetate content 19% (weight) 5
0 parts 50 parts of a mixture of glycidyl methacrylate-modified maleic acid resin and microcrystalline wax, P-
5 parts of menthane hydroperoxide were heated, melted, mixed and applied to paper at 160°C.

Baked for 10 minutes and then attached this to the plywood board and 160'c.
2%, heat seal for 15 seconds.

Even when this was placed in boiling water at 100° C. for 2 hours, no floating or peeling occurred, but those that were not baked did peel off.

Claims (1)

[Scope of Claims] 1 30 to 70 parts by weight of a base polymer, a polymerizable inorganic resin prepared by reacting a rosin resin having a functional group with a compound having a functional group bonding to the functional group and a polymerizable unsaturated double bond. 20 to 50 parts by weight of a tackifier containing 10 to 50 parts by weight of a rosin resin having a saturated double bond, and further 97,230 to 30 parts by weight if necessary, and 0 parts by weight of a polymerizable unsaturated monomer.
30 parts by weight of a hot melt resin composition. 2. A polymerizable unsaturated product obtained by reacting a rosin resin having a carboxyl group, a lower alkyl ester thereof, or a hydroxyl group with a compound having a functional group that reacts with a polymerizable unsaturated double bond and a carboxyl group, a lower alkyl ester thereof, or a hydroxyl group. The hot melt resin composition according to claim 1, which contains a rosin resin having a double bond.