JPH0873826A - Hot-melt adhesive composition - Google Patents

Abstract

PURPOSE: To obtain a hot-melt adhesive composition useful for inexpensive adhesive mats for catching mice, having little odor and rich in color stability, produced by melting and mixing a specific thermoplastic styrene-acrylic resin composition with a plasticizer and a thixotropic thickener in a specific ratio. CONSTITUTION: This hot-melt adhesive composition comprises (A) 100 pts.wt. of (i) a thermoplastic styrene-acrylic resin composition obtained by copolymerizing a styrene-based monomer containing a (meth)acrylic acid ester and/or (ii) 100 pts.wt. of the same recovered from used printed paper after being used as a toner for electronic photos (B) 10-150 pts.wt. of a plasticizer capable of plasticizing polystyrene and (C) 0.01-5 pts.wt. of >=1 thixotropic thickeners selected from a group consisting of a 12-30C hydroxy-higher fatty acid compound, a shellac resin, N-lauryl-L-glutamic acid-α,γ-di-n-butylamide, etc. The objective adhesive composition is produced by mixing and melting the component A with the components B and C. The component A has 2000-15000 number average molecular weight, >=300000 Z-average molecular weight, 50-600 of the ratio of the both and 50-120 deg.C glass transition temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in hot melt applicability because it has no melt flow property in the environment of room temperature to 40 ° C. and no stringiness or remarkable change in viscosity is observed during heating and melting at 150 to 200 ° C. The present invention relates to a styrene-acrylic resin-based hot-melt type pressure-sensitive adhesive composition which is excellent in weather resistance and hue stability and can be preferably used as a pressure-sensitive adhesive for rodent removal.

More specifically, it is a styrene-acrylic resin composition which is a glassy solid at room temperature formed by copolymerizing 50% by weight or more of a styrene-based monomer, and the same styrene as that used for so-called electrophotographic toner resins. A hot-melt pressure-sensitive adhesive composition comprising an acrylic copolymer resin as a base resin, a plasticizer capable of plasticizing polystyrene and a limited thixotropic agent.

[0003]

2. Description of the Related Art As is well known, hot-melt type pressure-sensitive adhesive compositions are more pollution-free than solvent-type pressure-sensitive adhesive compositions.
It is well known that it has advantages such as high coating speed during manufacturing, no need for solvent recovery equipment, no risk of fire, and no adverse effects on the atmosphere or the environment. ,
Therefore, its use is spreading widely in the adhesive industry.

Among the hot-melt type pressure-sensitive adhesive compositions, a styrene block type thermoplastic elastomer represented by styrene-isoprene-styrene block copolymer resin (hereinafter referred to as SIS) has styrene domains formed microscopically at room temperature. It is known that by doing so, the rigidity of the system can be exerted and high cohesive force and heat resistance can be given.

On the other hand, in the high temperature range above the glass transition temperature of polystyrene, the above composition melts and flows completely uniformly, so that hot melt coating can be easily carried out at a melting temperature of 130 to 190 ° C. ing.

In recent years, the base resin represented by SIS is
As a base resin for hot-melt type adhesives, it has become an important position, and SI is the hot-melt type adhesive.
It is no exaggeration to say that the S system is at the center of the market.

That is, the conventional typical hot melt type pressure sensitive adhesive composition is (1) a styrene block type thermoplastic elastomer represented by SIS as a base resin,
(2) A tackifier having a weight average molecular weight of at least several thousands selected from petroleum resin-based, rosin-based, rosin ester-based, terpene resin-based, etc., and (3) naphthene-based and / or paraffin-based as a softening agent. There is a composition composed of oil or a liquid tackifier resin which is a lower molecular weight substance of the above (2), and is widely used in the field of strong adhesives mainly in the field of adhesive labels and adhesive tapes.

For example, Japanese Patent Publication No. 1-47510 discloses, as (3), a SIS hot-melt pressure-sensitive adhesive composition which uses an ester compound of a higher alcohol and rosin as a softener component, and Japanese Patent Publication No. No. 28624, the same block-type thermoplastic elastomer as (1) above was copolymerized as the above-mentioned (2) component, especially a monomer mixture of isoprene, an aromatic monoolefin and an aliphatic monoolefin. Each of the hot-melt pressure-sensitive adhesive compositions has been proposed in which the obtained hydrocarbon resin system is further selected and used as the component (3), particularly naphthenic oil.

It is disclosed that each of the above compositions gives a tacky adhesive for paper diapers or a hot-melt adhesive composition of strong adhesive type having high adhesion properties to the base material of OPP or PET film. is there.

Further, in Japanese Patent Application Laid-Open No. 4-216890, the block type thermoplastic elastomer of SIS and / or its hydrogenated resin or styrene-butadiene-styrene block copolymer resin (hereinafter referred to as SBS) as the above (1). Has been proposed as a component in which a commonly known tackifier is used as the component (2) and an aliphatic liquid resin as the component (3). It discloses that it can be improved.

Therefore, it is widely known that the hot melt type pressure sensitive adhesive composition uses a styrene block type thermoplastic elastomer (also referred to as a styrene block type thermoplastic rubber) as a base resin.

However, according to these techniques, the styrene content is at most 45% by weight, and it is limited to the use of a rubber-like block type elastomer as the base resin, and the tackiness is basically in the low temperature to room temperature range. However, there was a problem that it was not exhibited at all.

The reason for this is described in detail in Japanese Patent Laid-Open No. 4-216890, and is generally understood as follows.

That is, in a hot-melt type pressure-sensitive adhesive composition comprising a base resin of a block type thermoplastic elastomer and a known tackifier and a softening agent, the interaction effect between the base resin and the tackifier and the softening agent is , For example, when a tackifier that is more compatible with the styrene domain phase than the rubber phase is selected and used, the styrene domain phase is reinforced and strengthened, and the composition exhibits almost no tackiness or only slightly tackiness. When a plasticizer based on dialkyl phthalate ester represented by dibutyl phthalate, which is known to dissolve in both phases, is selected and used, ,
It is said that only a composition in which no cohesive force is exhibited at room temperature is given.

Therefore, in the conventional SIS hot-melt pressure-sensitive adhesive composition, when an inexpensive plasticizer is selected and used as the softener component, the composition does not sufficiently exhibit the cohesive strength and heat resistance. In addition, there is a problem that only a composition having a significantly high room temperature flow property is provided, and a solution has been desired.

[0016] In general, SIS hot melt adhesive compositions have problems such as insufficient weather resistance, easy thermal decomposition, and lack of long term viscosity stability by heating and melting.

Most recently, improvements in adhesive creep properties,
That is, as a method for improving the adhesive cohesive force, for example, a hot-melt type pressure-sensitive adhesive composition in which a polymerizable ethylenic double bond group is introduced into the molecule to form a crosslinked structure by ultraviolet rays or electron beams, a so-called radical crosslinking type reactivity Hot-melt pressure-sensitive adhesive compositions, and so-called moisture-curable reactive hot-melt pressure-sensitive adhesive compositions containing an isocyanate group in the molecule have been investigated as solutions to the above problems.

However, it is still a very expensive composition,
On the other hand, when it is used in an adhesive field such as rat removal, it has a problem that it is unsuitable as a composition for mouse trapping because of its extremely low cohesive force retention strength, lacking adhesive extension properties, and extremely low capture rate.

Further, as a technique disclosed by paying attention to the problem of weather resistance of SIS resin, in JP-A-5-70754, a (meth) acrylic acid ester monomer and a relatively high glass are used as a SIS resin-like base resin. A polystyrene-grafted acrylic resin obtained by appropriately copolymerizing a macromer having a polystyrene segment in which one end of the polystyrene having a transition temperature ethylenic double bond is introduced,
Although a method of using a base resin for hot melt has been proposed, it has not been able to exhibit sufficient low temperature strong adhesion properties.

N is a kind of oil gelling agent for the purpose of improving the heat bleeding resistance of a hot melt composition containing a styrene block thermoplastic elastomer or a polyolefin resin as a base resin and containing a tackifier and a naphthenic oil. 0.01% of lauryl-L-glutamic acid derivative
The technology of adding and blending up to 1 wt.
No. 41 discloses that the exudation preventing property (bleeding resistance) of a liquid component is significantly improved without significantly changing the adhesive property of the hot melt composition.

However, in Japanese Patent Publication No. 62-301441, the composition of the tackifier and the softening agent is not compatible with the polystyrene domain phase of the base resin, but the composition is such that the tackifier and the softening agent are compatible with each other. And a tackifier component that is compatible with the polystyrene domain phase and /
Alternatively, when it is composed of a plasticizer component, the problem of insufficient cohesive strength has not been solved.

As described above, in the technology of the SIS base resin and its substitute base resin, and the composition containing naphthene oil used as a softening agent, the hot melt stability of the hot melt, the weather resistance, and the hue stability are generally However, many problems such as difficulty in reducing odor are inherent.

Generally, so-called excellent tackiness and elongation followability (capturing followability), which has a balance of tack force and cohesive force, enables small animals such as mice and cockroaches to be caught by one kind of hot-melt adhesive composition. As a hot-melt pressure-sensitive adhesive composition that satisfies both (reliability) and heat-resistant cohesive strength (heat-resistant flow) at the same time, most of the known hot-melt pressure-sensitive adhesive compositions for paper diapers and adhesive labels I'm not satisfied.

Therefore, in the system currently used as a hot-melt pressure-sensitive adhesive composition for exclusive use in rat harvesting, for example, 1 to 1 of polyisobutylene rubber having a weight average molecular weight of several hundred thousand or more.
One or a mixture selected from liquid terpene resin, naphthene oil, liquid polybutene, liquid polyisoprene or a hydrogenated product thereof, liquid polybutadiene or a hydrogenated product thereof, which has 0 wt% as a base resin and is sufficiently compatible with the base resin. In the present situation, by making the hot-melt composition containing 99 to 90% by weight as an essential component, excellent catch-following reliability and heat-resistant flowability are simultaneously satisfied, and at least 50% by weight of the styrene-based monomer is satisfied. From the above, no hot-melt pressure-sensitive adhesive composition using a random copolymer of 50% by weight or less of other monomers copolymerizable with styrene as a base resin is found.

On the other hand, obtained by randomly copolymerizing 50% by weight or more of a styrene-based monomer typified by styrene and the like and an acrylic-based monomer, which are inexpensively available on the market,
A hot-melt type composition containing a so-called thermoplastic styrene-acrylic resin or a mixed resin composition thereof as a base resin component is disclosed in, for example, JP-B-55-6895.
JP-B No. 58-40183 and the like are disclosed to be used as a toner binder for electrophotography.

However, even when a hot-melt type composition is prepared by using the thermoplastic styrene-acrylic resin composition as a base resin, there is no tack at room temperature, and these toner compositions are basically brittle glassy solids at room temperature. However, it is completely unsuitable as a hot melt adhesive composition for rat removal and paper diapers.

On the other hand, the Japanese Patent Publication No. 55-68
No. 95, Japanese Patent Publication No. 58-40183, and the like, a toner composition for electrophotography prepared from a thermoplastic styrene-acrylic resin and a resin composition thereof and a colorant,
It is used in large quantities, and as a result, a large amount of printed paper comes out, and from the waste paper that has finished printing, the toner resin composition is separated in high purity with the establishment of a paper recycling system in recent years. It is becoming possible to collect them, and their effective use is required. However, a thermoplastic styrene prepared as a toner for electrophotography, which is a hard solid at room temperature and has a glass transition temperature characteristic of 60 ° C. or higher,
There is no example of the use of an acrylic resin in a pressure-sensitive adhesive composition that exhibits sufficiently strong adhesive properties even in winter temperatures.

[0028]

DISCLOSURE OF THE INVENTION The object of the present invention is 45
No liquid dripping occurs even at a high temperature of ℃, 150-2
It has a low viscosity when melted at 00 ° C and is excellent in workability, long-term heating and heat stability, and the coating has excellent weather resistance, hue stability and low odor (no odor). Another object of the present invention is to provide a hot-melt pressure-sensitive adhesive composition that is excellent for use.

More specifically, it is a hot-melt type pressure-sensitive adhesive composition which satisfies particularly excellent mouse trap follow-up reliability and 45 ° C. heat resistant flowability, and has a styrene content of 50% by weight.
Random copolymer consisting of styrene-based vinyl monomer at low cost is manufactured at the same time, and at the same time, the thermoplastic styrene-acrylic copolymer-colorant mixed resin composition recovered in the solid paper recycling system is used as the base resin. However, it is an object of the present invention to provide a hot-melt pressure-sensitive adhesive composition which is suitable for low-priced rat-picking and has a strong adhesiveness and a good adhesion-adhesion followability.

[0030]

The inventors of the present invention have conducted extensive studies as a means for solving the above-mentioned problems, and as a result, a so-called electrophotographic toner resin was produced as a high styrene-acrylic copolymer resin in a large amount and at low cost. Focusing on the fact that it is available in the market, the specified resin for toner binder or the toner composition recovered from the specified waste paper for printing is used as the main base resin raw material, and is a plastic that can dissolve polystyrene. The present invention was accomplished by finding that the above-mentioned problems can be solved by using an agent and a specified thixotropic agent.

That is, the present invention is obtained by copolymerizing a styrenic vinyl monomer containing at least 50% by weight and at most 50% by weight or less of a styrenic monomer with an acrylic acid ester and / or a methacrylic acid ester. Has a molecular weight distribution of two or more peaks, and its number average molecular weight (M
n) is 2,000 to 15,000, Z average molecular weight (M
z) is 300,000 or more, Z-average molecular weight to number-average molecular weight ratio (Mz / Mn) is 50 to 600, and glass transition temperature is 50 to 120 ° C. thermoplastic styrene-acrylic resin, and / or electrophotographic toner. 10 to 150 parts by weight of a plasticizer capable of plasticizing polystyrene and the following (A) to (C) based on 100 parts by weight of the thermoplastic styrene-acrylic resin recovered after being used as a printed waste paper.
A hot-melt pressure-sensitive adhesive composition obtained by melt-mixing with 0.01 to 5 parts by weight of at least one thixotropic agent selected from the group consisting of: (A) A hydroxy higher fatty acid compound having an integer of 12 to 30 carbon atoms. (B) Slack resin. (C) N-lauryl-L-glutamic acid-α, γ-di-
n-Butylamide, N-lauryl-L-aspartic acid-α, γ-di-n-butylamide, N-stearyl-L
-Glutamic acid-α, γ-di-n-butyramide, N-
Stearyl-L-aspartic acid-α, γ-di-n-butyramide, N-lauryl-L-glutamic acid-α, γ
-One or a mixture of two or more selected from di-n-hexylamide.

The method for producing the hot-melt type pressure-sensitive adhesive composition of the present invention includes at least 50 to 50% of the styrene monomer.
95% by weight and one or more of acrylic acid ester and / or methacrylic acid ester 4.9 to 4
9.9% by weight and 0.1-10% by weight of methacrylic acid
A styrene-based vinyl monomer containing
A plasticizer which can be bulk polymerized to a polymerization rate of 30 to 70 wt% by heating to ℃ and then plasticize polystyrene.
A mercaptan-based chain transfer agent, a polymerization initiator and, if necessary, a solvent are further added to complete the polymerization reaction by solution polymerization in the same temperature range. A molecular weight polymer mixture was prepared, and the high molecular weight polymer and the low molecular weight polymer were mixed in a solid content weight ratio (30 to 90):
(70 to 10), and the number average molecular weight (Mn) of the mixed resin
Is 5,000 to 15,000, a Z-average molecular weight (Mz) is 300,000 or more, and a ratio Mz / Mn of the Z-average molecular weight and the number-average molecular weight is 50 to 600. It is prepared so that 10 to 150 parts by weight of a plasticizer capable of plasticizing polystyrene and 0.1 to 5 parts by weight of a thixotropic agent are added to 100 parts by weight of the plastic styrene-acrylic resin content. ~ 1
The present invention relates to a manufacturing method characterized by performing melt mixing at a temperature of 80 ° C.

The present invention also provides a pressure-sensitive adhesive mat for rodent removal, which is obtained by hot-melt coating the above hot-melt pressure-sensitive adhesive composition on one side of a cardboard substrate to a thickness of 50 to 500 μm, preferably 200 to 300 μm. It is provided.

The present invention will be described in more detail below.

In the following description, methacrylic acid ester and acrylic acid ester are collectively referred to as (meth) acrylic acid ester.

The object of the present invention is, as described in the item (objective) to be solved by the invention, a copolymer of a styrene-based vinyl monomer containing 50% by weight or more of the styrene-based monomer. To provide a hot-melt pressure-sensitive adhesive composition suitable for inexpensive rat removal by a production method capable of continuously producing a polymer, and after being provided as a toner resin mixed with a coloring agent for electrophotography, separated and recovered from used waste paper To provide an inexpensive hot-melt pressure-sensitive adhesive composition using the above resin as a base resin for rodent removal, and the composition does not cause dripping even at a high temperature of 45 ° C., When melted at 150 to 200 ° C., a composition having a low viscosity, excellent coating workability, long-term heat stability, hue stability, weather resistance, and low odor is provided.

The above-mentioned "when melted at 150 to 200 ° C, low-viscosity coating workability and long-term thermal stability" are more specifically: (a) softening point temperature in the range of 60 to 120 ° C. In
(B) The melt coating viscosity in the range of 150 to 190 ° C. is not more than 50,000 centipoise, preferably not more than 30,000 centipoise, more preferably not more than 20,000 centipoise as a low shear viscosity value measured by a B-type viscometer. (C) It means that the change in melt viscosity under the condition of (B) for 24 hours is within ± 10%.

In the present invention, the above-mentioned "150-20"
The low-viscosity coating workability at the time of melting at 0 ° C. is excellent and the long-term heat stability ”means that the following thermoplastic styrene-acrylic resin is used as a base resin and further contains a plasticizer and a thixotropic agent described below. Is specifically achieved in.

In the following description, thermoplastic styrene-
The acrylic resin refers to a mixed resin composition of two or more kinds.

That is, the thermoplastic styrene-acrylic resin of the present invention is a so-called styrene comprising at least 50% by weight of styrene and one or more (meth) acrylic acid ester monomers of 50% by weight or less. Which is a glassy solid at room temperature and has a number average molecular weight (Mn) of 2,000 to 15,000, which has a molecular weight distribution of two or more peaks and is obtained by copolymerizing a vinyl vinyl monomer.
Preferably, it is 2,000 to 10,000, and Z average molecular weight (Mz) is 300,000 or more, preferably 400,0.
00 or more, the ratio of Z-average molecular weight to number-average molecular weight Mz /
The resin composition has Mn of 50 to 600, preferably 50 to 350.

The above resin composition is already on the market in large quantities as one type of toner binder resin for electrophotography. Therefore, of the above resin compositions prepared as the toner binder resin for electrophotography, any composition having a matching molecular weight distribution and average molecular weight can be preferably used.

The preferred thermoplastic styrene-acrylic resin of the present invention is a so-called styrene-based resin comprising at least 50% by weight of a styrene-based monomer and one or more (meth) acrylic acid ester of 50% by weight or less. It is essential that the vinyl monomer is randomly copolymerized.

A more preferred thermoplastic styrene-acrylic resin is a styrene-based vinyl monomer containing at least 50% by weight of styrene or α-methylstyrene and at most 50% by weight of (meth) acrylic acid ester. It is a mixture of a high molecular weight polymer (hereinafter simply referred to as a high molecular weight polymer) and a low molecular weight polymer (hereinafter simply referred to as a low molecular weight polymer) obtained by copolymerizing a polymer, and a mixture thereof. Has a number average molecular weight (Mn) of 2,000 to 10,000.
0, Z average molecular weight (Mz) is 400,000 or more, Z
Ratio (Mz / Mn) of average molecular weight and number average molecular weight is 50 to
350, the glass transition temperature is 70 to 100 ° C, more preferably 70 to 85 ° C.

An even more preferred thermoplastic styrene-acrylic resin of the present invention is at least 50% by weight and at most 50% by weight (meth) of the styrene monomer.
A styrene-based vinyl monomer containing an acrylic ester is subjected to bulk polymerization at a polymerization rate of 30 to 90% by weight, and then a ratio of the plasticizer capable of plasticizing polystyrene to the total amount of the charged monomers is 0. A high molecular weight polymer obtained by a so-called two-stage polymerization method, which was obtained by additionally adding 01 to 1% by weight of a divinyl compound and a polymerization initiator to lower the viscosity to complete the solution polymerization, and the styrene-based polymer separately The number average molecular weight Mn obtained by polymerizing a vinyl monomer by a solution polymerization method is 1,000.
It is a mixed resin composition with a low molecular weight polymer of up to 5,000, and is preferable in that the hot-melt pressure-sensitive adhesive composition of the present invention can be obtained at low cost.

Further, the thermoplastic styrene-acrylic resin contains at least 50% by weight and at most 49.9% by weight or less of the styrene-based monomer, and further 0.1 to 10% of acrylic acid ester and / or methacrylic acid ester. A styrene-based vinyl monomer containing wt% methacrylic acid is bulk polymerized up to a polymerization rate of 30 to 70 wt%, and then a plasticizer or solvent capable of plasticizing polystyrene,
A so-called two-stage polymerization method obtained by additionally adding a divinyl compound in an amount of 0.01 to 1% by weight in the total charged monomers and a polymerization initiator to further reduce the viscosity and complete the solution polymerization. Number average molecular weight M obtained by polymerizing the styrene vinyl monomer separately from the high molecular weight polymer obtained by
n is a mixed resin composition with a low molecular weight polymer having a molecular weight of 1,000 to 5,000, and the resin composition is used for non-toner, which means that the hot melt adhesive composition of the present invention is heat resistant. It is preferable because it has a good balance of flowability and coating workability.

Further, the thermoplastic styrene-acrylic resin is styrene and / or α-methylstyrene of 60 to 60%.
95% by weight, having a radically polymerizable unsaturated bond group at one end and having a ratio Mw / Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2 or less and a weight average molecular weight (Mw) of 1,000. Of 0.5 to 20% by weight of acrylonitrile macromer with so-called polyacrylonitrile segments, 4.5 to 39.5% by weight of (meth) acrylic acid ester, and 0 to 10% by weight of A styrene vinyl monomer containing methacrylic acid is subjected to bulk polymerization at a polymerization rate of 30 to 70% by weight, and then a plasticizer or solvent capable of plasticizing polystyrene, a polymerization initiator, and methacrylic acid are styrene. Only when it is not present in the system vinyl monomer, 0.01 to 1% by weight of the divinyl compound is added to the total amount of the charged monomers, and the system is added. A number average molecular weight Mn obtained by separately polymerizing the styrene vinyl monomer by a solution polymerization method with a high molecular weight polymer obtained by a so-called two-step polymerization method, which is obtained by lowering the viscosity and completing the solution polymerization. Is 1,000 to 5,0
00 is a mixed resin composition with a low molecular weight polymer of
The hot-melt pressure-sensitive adhesive composition of the present invention is preferable because it has the action and effect excellent in heat-resistant cohesive force.

Furthermore, the thermoplastic styrene-acrylic resin is 49.5 to 89.5% by weight of the styrene monomer.
And a weight average molecular weight (M
w) and the number average molecular weight (Mn) ratio Mw / Mn is 2 or less and the weight average molecular weight (Mw) is 1,000 to 15,000.
0.5 to 20% by weight of polystyrene macromer having so-called polystyrene segments in the range of 0, 4.4 to 40% by weight of (meth) acrylic acid ester, and 0.1 to 10% by weight of methacrylic acid. A styrene-based vinyl monomer is subjected to bulk polymerization at a polymerization rate of 30 to 70% by weight, and then a plasticizer or solvent capable of plasticizing polystyrene and a ratio of 0.0 in the total charged monomers.
Obtained by additionally adding 1 to 1% by weight of a divinyl compound and a polymerization initiator to reduce the viscosity of the system and complete solution polymerization.
A high molecular weight polymer obtained by the so-called two-step polymerization method,
The present invention is a mixed resin composition with a low molecular weight polymer having a number average molecular weight Mn of 1,000 to 5,000, which is obtained by separately polymerizing the styrene vinyl monomer by a solution polymerization method. It is preferable because the workability of stringing and coating the hot melt pressure sensitive adhesive composition is improved.

The thermoplastic styrene-acrylic resin of the present invention is melt-mixed in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and is used as a toner for electrophotography. Resin 10 separated and collected
1 of coloring agents represented by carbon black for 0 parts by weight
˜20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight, most preferably 1 to 5 parts by weight, a so-called recovered toner is used for effective use of resources. Is preferred.

Further, the thermoplastic styrene-acrylic resin is
As described above, it is a mixture containing a polymer and a low molecular weight polymer, and the polymer has a styrene vinyl monomer polymerization rate of 30.
Up to 70% by weight can be obtained by bulk polymerization, and then a plasticizer capable of plasticizing polystyrene and a polymerization initiator are additionally added to lower the viscosity to complete the solution polymerization, while the low molecular weight substances are separately or the same. The solution is obtained by the third-stage solution polymerization method in a kettle, and the mixing ratio is finally (30 to 90) :( 70 to 10), preferably (30 to 90) in terms of solid content weight ratio of polymer: low molecular weight. 80) :( 70-20), more preferably (30-70) :( 70-30), and most preferably (40-70) :( 60-30). It is most preferable because the melt work viscosity and the adhesive property are easily satisfied at the same time.

Further, the number average molecular weight M of the above low molecular weight substance.
Copolymerized with a styrene-based vinyl monomer having n of 1,000 to 5,000 and containing at least 50% by weight and at most 50% by weight or less of (meth) acrylic acid ester of the styrene-based monomer. Is.

The low molecular weight substance which is one component of the thermoplastic styrene-acrylic resin of the present invention means at least 50% by weight or more and at most 50% by weight or less of (meth) acrylic acid ester of the styrene monomer. A typical example is one obtained by completing solution polymerization in one step using a styrene-based vinyl monomer contained therein.

In the thermoplastic styrene-acrylic resin of the present invention, as described above, it is sufficient to use a high molecular weight alone or a molten mixture of the high molecular weight and the low molecular weight.
For high molecular weight polymers, a styrene vinyl monomer is used at a polymerization temperature of 6
Bulk polymerization is performed at 0 to 160 ° C. for a polymerization rate of 30 to 90% by weight, preferably 40 to 80% by weight, and more preferably 50 to 70% by weight, and then a plasticizer and a polymerization initiator are additionally added. It is preferable to use a polymer composition having a Z-average molecular weight of 300,000 or more, which is produced by a two-step polymerization method or a multi-step polymerization method in which solution polymerization is continued at a polymerization temperature of 60 to 160 ° C.

The reason is that when the Z-average molecular weight of the high-molecular weight polymer is 300,000 or less, the cohesive force of the obtained hot-melt pressure-sensitive adhesive composition is lowered and the thixotropic property is in a range not so much lowering the adhesive property. This is because the addition of the imparting agent does not improve, and often causes a problem that only a composition having extremely high flowability can be obtained at room temperature to 50 ° C. Therefore, it is necessary to naturally use a large amount of thixotropic agent in order to sufficiently solve the flow property, and as a result,
This is because the strong adhesive property (low temperature tack force) at low temperature and the reliability of tracking rat extension elongation are extremely reduced.

On the other hand, the low molecular weight product may be a styrene-based vinyl monomer obtained by a known method,
There are no particular restrictions, but it is sufficient to complete the polymerization of the styrene vinyl monomer by, for example, a bulk polymerization method or a solution polymerization method,
As a method that can be obtained at low cost, the polymerization temperature is 190 to
The thing obtained by the solution polymerization method of 30 degreeC is the most preferable.

In the thermoplastic styrene-acrylic resin of the present invention, it is preferable that a high molecular polymer and a low molecular polymer are blended in a solid content weight ratio of (30 to 90) :( 70 to 10). More preferably (30-80): (70-2
0), most preferably (50-85): (50-20)
Is. The reason is that when the proportion of the high molecular weight polymer in the resin is 30% by weight or less, the cohesive force of the obtained hot-melt adhesive composition becomes extremely low, and when it is 90 parts by weight or more, the obtained hot-melt adhesive composition. This is because the product becomes too viscous.

The thermoplastic styrene-acrylic resin of the present invention which is a mixture has a number average molecular weight (Mn) of 2,000 to 15,000 and a Z average molecular weight (Mz) of 300,000 or more. More preferably 40
The ratio Mz / Mn of the Z-average molecular weight to the number-average molecular weight of 50,000 or more is in the range of 50 to 600, preferably 50 to 3
Setting the range to 50 is extremely important for obtaining the hot-melt pressure-sensitive adhesive composition of the present invention, and the reason will be described below.

That is, Mn is 2,000 or less and M
This is because when the z / Mn ratio is 30 or less, the finally obtained hot-melt pressure-sensitive adhesive composition lacks heat-resistant flow characteristics and causes liquid sagging over time (the problem of heat-resistant flow property at 45 ° C.).

On the other hand, Mn is 15,000 or more and Mz
When the / Mn ratio is 600 or more, the thermoplastic fluidity is almost lost near the melting temperature of 180 ° C. which is a general coating temperature when finished as the composition of the present invention, and the optimum target work melt viscosity of the present invention is This is because it exhibits a viscosity far exceeding 50,000 centipoise mentioned above, and thus the coating workability is poor.

Particularly in the present invention, the thermoplastic styrene-acrylic resin has a high molecular weight of 6 even if the glass transition temperature is low.
From the gist of the present invention, it is highly preferable to use a glassy solid having a temperature of 0 ° C. or higher and a glassy solid having a low glass transition temperature of 70 ° C. or higher even if the low molecular weight substance has a low glass transition temperature.

In the thermoplastic styrene-acrylic resin of the present invention, as described above, it is important that the Z-average molecular weight is at least the specified value. If the thermoplastic styrene-acrylic resin has an Mz of more than 300,000, the hot melt adhesive composition of the present invention is characterized by sufficient heat cohesive strength, which is a main purpose, and appropriate tack and adhesive elongation followability. The rate of supplementation to parent mice is high throughout the year.

Generally, as a method for producing a high molecular weight compound having a large Mz, polymerization is carried out by a solution polymerization method in the presence of a solvent and a polymerization initiator at a low temperature to reduce the polymerization rate, thereby producing a polymer having a large Z-average molecular weight. Methods of obtaining coalescence are known. However, in this method, it takes a long time to obtain a sufficiently large Z-average molecular weight by low-temperature polymerization, the productivity is extremely poor, and the cost is high. Therefore, although there is no problem in adopting this method as a method for obtaining the high molecular weight polymer of the thermoplastic styrene-acrylic resin used in the present invention, it is not a very preferable method.

Therefore, as a preferred method for producing the polymer composition of the present invention, 60 to 14 styrene vinyl monomers are used.
After performing polymerization by bulk polymerization at a temperature of 0 ° C. to a high polymerization rate, a necessary amount of plasticizer, and xylene, toluene, and
A low boiling point solvent represented by cyclohexane is added, a polymerization initiator is additionally added, and the second-stage solution polymerization is completed, so that a so-called known two-stage polymerization method can be adopted to continuously produce the resin at low cost. From the viewpoint, it can be mentioned as a preferable method.

Among other known polymerization methods for the purpose of increasing the molecular weight of the high molecular weight material, suspension polymerization method and emulsion polymerization method are generally well known. Since water as the dispersion medium and the polymer particles coexist with each other, it is difficult to sufficiently remove the emulsifier and the dispersant, and it is even more difficult to uniformly control the removal of these impurities.

Therefore, in the high molecular weight polymer of the thermoplastic styrene-acrylic resin obtained by the known suspension polymerization method or emulsion polymerization method, the colorless hue stability and the hot melt viscosity which are the object of the present invention are long-term. This is not a preferred method in the present invention because it has problems such as insufficient stability and weather resistance.

Further, by the bulk polymerization method and the solution polymerization method,
Mz / Mn, which is a so-called completely soluble type non-crosslinked polymer that does not cause insoluble matter in tetrahydrofuran or a plasticizer which is an essential component of the present invention
As a polymerization method for obtaining a resin similar to the resin mixture of the present invention having a large ratio of 30 to 90% by weight of the initial charged monomer,
Until the bulk polymerization is carried out at a temperature of 60 to 150 ° C., then a low boiling point solvent is added to reduce the viscosity of the system, a polymerization initiator is further added to complete the polymerization, and the solvent is removed at the same temperature.
A method for producing a solvent-free binder resin composition for a toner for electrophotography is well known, and there is no problem in producing by the method.

However, in this synthetic method, no example of the presence of a plasticizer capable of plasticizing or dissolving polystyrene in the second stage solution polymerization is found in the production of known toner resins, and in the solution polymerization. There was no report of whether or not the presence of a plasticizer gives a high Mz molecular weight. However, as a result of various examinations, no matter what kind of solution polymerization method using the plasticizer, the objective resin according to the present invention was obtained. It turned out to be synthesized. Therefore, it was revealed that the production of the base resin and the final production of the pressure-sensitive adhesive composition can be carried out in the same pot, and this production method / method is extremely important as a method for providing the composition of the present invention at a low cost.

That is, one of the preferred methods for producing the polymer of the present invention is a system containing a known plasticizer capable of plasticizing or dissolving polystyrene in the same pot for producing the above-mentioned thermoplastic styrene-acrylic resin. After the thermoplastic styrene-acrylic resin for non-toner of the present invention is produced by a two-step polymerization method, the above-mentioned book prepared by optionally adding a plasticizer and a thixotropic agent described below by heat mixing. The manufacturing method of the invention is a preferable method because it can reduce the cost. In particular, in a known method for polymerizing a binder resin for an acrylic toner, a low boiling point solvent is said to be essential in a solution polymerization field, and therefore, when a solid is finally taken out,
This is because the solvent removal step is essential. This is because it is clear that the solvent removal step can be omitted in the method for producing a hot-melt pressure-sensitive adhesive composition of the present invention described above, and that it can be produced inexpensively in a batch system or a continuous system.

The styrenic vinyl monomer in the present invention is one kind selected from at least 50% by weight or more of styrenic monomer and 50% by weight or less of (meth) acrylic acid ester. Alternatively, it refers to a monomer mixture containing two or more kinds of monomer components.

Styrene-based monomers include styrene,
Examples include α-methylstyrene, vinyltoluene, chlorostyrene, isopropenylphenol, isopropenylbenzyl isocyanate, isopropenyldimethylbenzyl isocyanate, o, m, p-methylstyrene and the like. Preferred are styrene and α-methylstyrene.

The (meth) acrylic acid ester is a methacrylic acid ester and / or an acrylic acid ester, and typical examples of the acrylic acid ester include, for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, octyl acrylate, cyclohexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl acrylate, dimethylaminomethyl acrylate, Acrylic acid dimethylaminoethyl ester is mentioned.

On the other hand, as the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate,
Typical examples are furfuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, dimethylaminomethyl methacrylate ester, and dimethylaminoethyl methacrylate ester.

The styrenic vinyl monomer of the present invention contains a monomer other than those mentioned above in a range not exceeding 10% by weight, more preferably not exceeding 5% by weight, and even more preferably not more than 0. There is no problem to use it in the range of 1 to 3% by weight, and typical examples thereof include unsaturated fatty acid diesters such as dibutyl maleate, dioctyl maleate, dibutyl fumarate, dioctyl fumarate, vinyl acetate and propion. Vinyl esters such as vinyl acrylate,
Acrylonitrile, nitrogen-containing vinyl monomers such as methacrylonitrile, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, cinnamic acid, maleic acid, maleic anhydride,
Fumaric acid, unsaturated dicarboxylic acids such as itaconic acid, monobutyl maleate, monooctyl maleate, monobutyl fumarate, monoalkyl ester monomers of unsaturated dicarboxylic acids such as monooctyl fumarate, styrene sulfonic acid, acrylamide, Methacrylamide, N-substituted acrylamide, N-substituted methacrylamide, and acrylamidopropanesulfonic acid.

Further, as a special example, polyacrylonitrile having a weight-average molecular weight of less than 10,000, having a vinyl group capable of radical polymerization at one end, the same poly-silicon, the same polystyrene, the same polybutyl acrylate, the same polymethyl methacrylate, and the same polystyrene. And a polymer having a so-called macromer, which is commonly referred to as the above-mentioned, is particularly preferable. Among them, the macromer in which the radical-polymerizable functional group at one end is a (meth) acryloyl group is a preferable example. 20 in vinyl monomer
There is no problem in using it in a range not exceeding 5% by weight, preferably not exceeding 10% by weight, and more preferably not exceeding 5% by weight.

In the present invention, preferred styrene-based vinyl monomers at the time of producing the high molecular weight product are 50 to 85% by weight of styrene and / or α-methylstyrene, and 0.1 to 3% by weight. % Methacrylic acid and 12-49.
It is very preferable to have a monomer composition consisting of 5% by weight of 2-ethylhexyl acrylate and / or n-butyl acrylate. The reason is that the Mz of the polymer is 400,
This is because it is easy to set it to 000 or more.

Further, in the present invention, the most preferable styrene vinyl monomer at the time of producing a high molecular weight substance is 60 to 95% by weight of styrene and / or α-methylstyrene.
And having a (meth) acryloyl group at one end and having a ratio Mw / Mn of weight average molecular weight (Mw) and number average molecular weight (Mn) of 2
And the weight average molecular weight (Mw) is 1,000 to 3
0.5 to 20% by weight of acrylonitrile macromer having a so-called polyacrylonitrile segment in the range of 10,000 and 4.5 to 39.5% by weight of (meth) acrylic acid ester, and 0 to 10% by weight. An example is a monomer composition containing methacrylic acid. The reason is that the Mz of the high molecular weight compound is 400,000 or more and the ability of polyacrylonitrile to form a microdomain structure can be expected, and the thixotropic effect and heat resistance effect are most prominent.

In the present invention, when a high molecular weight polymer is produced using the styrene vinyl monomer, bulk polymerization is carried out at a temperature of 60 to 150 ° C. without using a polymerization initiator, and then a plasticizer is used. A method in which a so-called two-step polymerization method or a multi-step polymerization method in which a polymerization initiator is added and solution polymerization is completed to complete the polymerization is preferable.

In general, the Mz of the polymer obtained at that time is largely controlled by the polymerization rate. Therefore, in order to obtain a polymer having a large Mz, the polymerization rate in bulk polymerization is 30 to 90% by weight, preferably 40% by weight.
The most important point is to proceed to a polymerization method without a polymerization initiator up to 85% by weight, more preferably 40 to 80% by weight. This is because if the polymerization rate is less than 30% by weight, an increase in Mz cannot be expected, and if it exceeds 90% by weight, the viscosity of the system remarkably increases, which causes difficulty in production.

Termination of bulk polymerization is accomplished by methods such as simply cooling once or adding a cold plasticizer. The use of a solvent in combination or in place of the cold plasticizer is also included in the production method of the present invention. When a solvent is used, it is achieved by removing the solvent after completion of the polymerization and substituting the complete plasticizer.

Solution polymerization after bulk polymerization is usually carried out at a temperature of 6
It is carried out at 0 to 150 ° C., but it is not particularly limited as long as the purpose is achieved even if it is outside the above temperature range for the purpose of controlling the molecular weight. The solution polymerization is initiated by continuously or intermittently adding a polymerization initiator uniformly dissolved in a plasticizer over 1 to 20 hours, but the addition of the addition causes a large change in the concentration of the polymerization initiator. However, continuous addition is more preferable because the reproducibility of the molecular weight tends to be slightly lacking.

As the polymerization initiator described in the present invention, all known compounds can be used.

Specific examples are 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (2,2'-azobis (2,4-dimethylvaleronitrile). 4-dimethylvaleronitrile), 2,2'-
Azobis (2-methylbutyronitrile), dimethyl-
2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo 2,2'-dimethyl-4-methoxyvaleronitrile ,
Azo initiators such as 2,2′-azobis (2-methylpropane), ketone peroxides such as methylethylketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-Trimethylcyclohexane, 2,2-bis (t-butylperoxy)
Peroxyketals such as butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di Dialkyl peroxides such as (t-butylperoxy) hexane and α, α′-bis (t-butylperoxyisopropyl) benzene, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, Benzoyl peroxide, diacyl peroxides such as m-toluoyl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, dimethoxyisopropylate Peroxydicarbonates, peroxydicarbonates such as di (3-methyl-3-methoxybutyl) peroxydicarbonate, sulfuryl peroxides such as acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t- Butyl peroxyisobutyrate, t
-Butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxy isopropyl carbonate and other peroxy esters Etc. are illustrated. Although not particularly limited, the above-mentioned polymerization initiator may be usually used in the range of 0.01 to 10 parts by weight per 100 parts by weight of the charged monomer, so that the intended high or low molecular weight product can be obtained. It is customary to select the weight part to be used.

By the method described above, the high molecular weight M
Although the thermoplastic styrene-acrylic resin of the present invention having z of 300,000 or more can be sufficiently produced, it will be described below as a more preferable method for preparing a base resin having an even higher Mz.

After the cold plasticizer was added at the end of bulk polymerization,
At the time of solution polymerization, the ratio of all charged monomers is 0.0
A more preferable and general method is a method of producing by using the following divinyl compound copolymerizable with styrene in the range of 1 to 1% by weight.

By the solution polymerization method in the presence of a small amount of divinyl compound, it is possible to obtain a large copolymer resin having Mz soluble in the plasticizer without causing a three-dimensional crosslinking reaction.
This method is preferable because it gives a preferable result of Mz of 450,000 or more. When the amount of the divinyl compound monomer is more than 1 part by weight, a non-crosslinked polymer cannot be obtained, and a considerable amount of insoluble resin is produced in the gelled tetrahydrofuran or the plasticizer, which is not preferable.

Typical examples of the divinyl compound according to the present invention include the following, which are copolymerizable with styrene.

That is, for example, in addition to divinylbenzene and ethylene glycol diacrylate, in addition to (poly) ethylene glycol diacrylate and propylene glycol diacrylate represented by diethylene glycol diacrylate, triethylene glycol diacrylate and nonaethylene glycol diacrylate, (Poly) propylene glycol diacrylate represented by dipropylene glycol diacrylate, tripropylene glycol diacrylate, nonapropylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, nonaethylene glycol diacrylate (Poly) represented by methacrylate, etc.
Polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, (poly) propylene glycol dimethacrylate represented by dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, etc., bisphenol A and / or F type epoxy Examples thereof include diacrylate and ethylene bisacrylamide, and divinylbenzene, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate are preferable.

Still another polymerization method for increasing the Mz of the polymer which is one component of the thermoplastic styrene-acrylic resin of the present invention is as follows. It is also possible to use 1 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight of methacrylic acid.

At this time, it is essential to use methacrylic acid in bulk polymerization, and even if it is added and used after bulk polymerization, there is no effect of increasing Mz. For some reason, acrylic acid and maleic acid do not have the same effect.

The low molecular weight substance shown as one component of the thermoplastic styrene-acrylic resin of the present invention, that is, the resin alone has a Mn value of 1,000 to 5,000, preferably 1,500 to 3,000. As a typical manufacturing method, the following methods are typical.

That is, it is preferable to employ a solution polymerization method capable of reducing impurities as much as possible, and the molecular weight can be controlled by controlling the concentration of styrene vinyl monomer and its composition ratio, the type of plasticizer and its addition concentration, and the known chain transfer agent. It is possible to set by the addition amount, the amount and type of radical initiator, the polymerization reaction temperature and the like.

The styrenic vinyl monomer of the present invention used in the production of the low molecular weight product is as described above.

Particularly preferred as styrene is 50% by weight.
The above-mentioned styrene vinyl monomer is contained.

The polymer of the present invention contains a high molecular weight polymer and a low molecular weight polymer, and the average Mn value of the mixture is 2,000 to 1.
50,000 and the same average (Mz / Mn) is 50 to 60
It is particularly preferable that the mixture is heated and mixed so that the average (Mz / Mn) is 0, preferably 50 to 350.

Due to the presence of the low-molecular weight substance, the hot-melt pressure-sensitive adhesive composition of the present invention has a working viscosity at the time of heat-melting in a target viscosity range, and when it is continuously hot-melt coated on a cardboard,
This is because it has the advantage of being able to prevent the stringiness and ensuring appropriate hot tack and fluidity (which is preferable in the sense of being excellent in coating workability).

In the production of the low molecular weight polymer of the thermoplastic styrene-acrylic resin of the present invention, a particularly preferable polymerization temperature is 190 to 230 ° C.

The glass transition temperature of the low molecular weight substance of the present invention alone is preferably at least 50 ° C. or higher.
When the temperature is lower than 0 ° C, it cannot be used at all, but it is necessary to make the monomer composition in which the content of inexpensive styrene is greatly reduced. The reason is that there is a problem in manufacturing cost and there is no actual record as a resin for toner.

Generally, it is possible to produce the same low molecular weight polymer as described above by the batch charging method at a polymerization temperature of 190 ° C. or less by using a large amount of a radical initiator in the presence of a large amount of solvent. However, it is not recommended in the present invention because a large amount of polymerization initiator residue remains in the system and productivity is low.

Further, a method for producing the low molecular weight compound of the present invention using a known mercaptan chain transfer agent is also recommended.

As the mercaptan chain transfer agent, n-
Dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, mercaptopropionic acid, etc. are well known and can be preferably used, and are highly preferable as a method for producing the thermoplastic styrene-acrylic resin of the present invention at a low cost.

Therefore, in the above-mentioned polymerization method using a chain transfer agent, the desired low molecular weight product can be obtained by using the required amount of mercaptan chain transfer agent under the polymerization temperature condition of 160 to 230 ° C.

The thermoplastic styrene-acrylic resin of the present invention includes Mz, Mn and Mz / Mn among those already marketed for electrophotographic toners, in addition to the above-mentioned method.
Can be preferably used as long as the toner composition is within the range described in the present invention. A so-called styrene-based vinyl monomer is used to obtain a polymerization rate of 30 to 90% by bulk polymerization, and then a solvent and a radical initiator are added. After adopting the two-step polymerization method to complete the solution polymerization, the product is finally taken out through a solvent removal step such as flashing, and a commercially available product of the resin finely pulverized for toner is also available. Or any of the resins prepared separately or a mixture thereof,
Finally, there is no problem even if these resins are heat-melted and the plasticizer and the thixotropic agent are heat-melt mixed to prepare the hot-melt pressure-sensitive adhesive composition of the present invention.

As the plasticizer capable of plasticizing the polystyrene of the present invention, there is no problem as it is a known plasticizer, but from the viewpoint of easy availability, the aromatic dicarboxylic acid dialkyl ester represented by phthalic acid dialkyl ester is particularly preferable. And fatty acid dialkyl esters represented by adipic acid dialkyl ester and azelaic acid dialkyl ester are preferable.

More preferably, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-n-butyl phthalate, dinonyl phthalate, diheptyl phthalate, ditridecyl phthalate, adipic acid di- One or two kinds selected from 2-ethylhexyl and azelaic acid-di-2-ethylhexyl are preferable.

It is particularly preferable to use one of di-2-ethylhexyl phthalate, di-n-octyl phthalate and di-n-butyl phthalate.

The proportion of the plasticizer used in the hot-melt pressure-sensitive adhesive composition of the present invention is such that the thermoplastic styrene-
10 to 150 parts by weight, preferably 20 to 150 parts by weight, and more preferably 3 to 100 parts by weight of the acrylic resin.
It is 0 to 120 parts, and most preferably 30 to 80 parts.

100 of thermoplastic styrene-acrylic resin
If the plasticizer is less than 10 parts by weight with respect to parts by weight, the tackiness is not exhibited, and if it is more than 150 parts by weight, the plasticization is excessive and the cohesive force and the flow property are poor, and the supplementary extension of the rodent at 40 ° C. This is because the melt viscosity is extremely low and the workability of hot melt coating for securing a thick film is poor.

The thixotropic agent of the present invention includes the following (A)
Selected from (C). (A) A hydroxy higher fatty acid compound having an integer of 12 to 30 carbon atoms, particularly preferably hydroxystearic acid having 18 carbon atoms. (B) Slack resin. (C) N-lauryl-L-glutamic acid-α, γ-di-
n-Butylamide, N-lauryl-L-aspartic acid-α, γ-di-n-butylamide, N-stearyl-L
-Glutamic acid-α, γ-di-n-butyramide, N-
Stearyl-L-aspartic acid-α, γ-di-n-butyramide, N-lauryl-L-glutamic acid-α, γ
1-di-n-hexylamide, particularly preferably N-lauryl-L-glutamic acid-α, γ-di-
Either n-butylamide or N-lauryl-L-glutamic acid-α, γ-di-n-hexylamide.

The hydroxy higher fatty acid compound having an integer of 12 to 30 carbon atoms (A) is a hydroxy fatty acid represented by an integer of 12 to 30 carbon atoms and containing at least one hydroxyl group in the molecule. Hydroxymyristic acid, hydroxypalmitic acid, hydroxystearic acid and the like can be mentioned, with hydroxystearic acid being a particularly preferred example.

By using the above thixotropic agent in the hot melt pressure-sensitive adhesive composition of the present invention in an amount of 0.01 to 5 parts by weight, preferably 0.5 to 3 parts by weight,
In the composition, it is an essential constituent because it can impart a proper flow improving property to the composition in the temperature range from cold to 50 ° C. without significantly deteriorating the strong adhesive property.

The above-mentioned thixotropic agent is uniformly compatible with each other when heated, and the melted and extruded product solidifies from the molten state, and at the same time, the hydrogen-bonding ability of the composition is probably due to the strong intermolecular interaction of the thixotropic agent. It is considered that bleeding resistance and flow prevention effect at a temperature of less than 50 ° C. are exhibited.

The thixotropic agent exhibits a monomolecular behavior by dissociation of hydrogen bonds at a melting temperature of more than 120 ° C. Therefore, the workability of melt-coating the hot-melt pressure-sensitive adhesive composition of the present invention is thixotropic. The presence of the agent does not cause any problems. However, the use of a thixotropic agent in an amount of more than 5 parts by weight is not included in the scope of the present invention because it adversely affects the adhesiveness of the composition.

The hot-melt pressure-sensitive adhesive composition of the present invention may be used in combination with the following publicly known tackifiers for the purpose of adjusting low-temperature adhesion properties, adjusting melt viscosity and reducing costs.

As typical tackifiers that can be used,
For example, (hydrogenated) aromatic or aliphatic petroleum resin, terpene resin, terpene-phenol copolymer resin, (hydrogenated) rosin and (hydrogenated) rosin ester resin, polymerized rosin,
In addition to hydrogenated dicyclopentadiene resin, 100% styrene resin, coumarone-indene resin, ketone resin, xylene resin, etc., C5 such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha
C5 petroleum resin obtained by copolymerizing fractions, C9 petroleum obtained by copolymerizing C9 fractions such as indene, vinyltoluene, α or β-methylstyrene produced by thermal decomposition of petroleum naphtha A resin, a copolymerized petroleum resin of the C5 fraction and the C9 fraction, and the like are typical, and a known tackifier having a weight average molecular weight in the range of 400 to 3,000 is preferable.

One or more of them may be used in combination in the hot-melt pressure-sensitive adhesive composition of the present invention in a maximum amount of 20% by weight or less, preferably 10 parts by weight or less.

In addition, the hot-melt pressure-sensitive adhesive composition of the present invention contains known heat-aging inhibitors, ultraviolet absorbers, ultraviolet stabilizers, metal deactivators, fillers, organic substances, inorganic substances, Used in titanate-based and / or silane-based coupling agents, waxes, already known, for example, styrene block-based thermoplastic polymers and general solvent-based adhesives that are completely soluble in the plasticizer used in the present invention. The known thermoplastic acrylic rubber, styrene-butadiene rubber, chloroprene rubber, ionomer resin and the like can be used within a range that does not significantly impair the effects of the present invention.

Particularly, in the hot-melt pressure-sensitive adhesive composition of the present invention, examples of the ultraviolet absorber include 2-5-methyl-2.
-Hydroxyphenyl) benzotriazole, 2- [2
-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro Benzophenol, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole-based compounds such as benzotriazole,
2-Ethoxy-2'-ethyloxazolic acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl oxac acid bisanilide and other oxazoic acid amide compounds, 2,4-hydroxy- Four
When 0.1 to 3% by weight of a benzophenone compound such as octoxybenzophenone is used, the weather resistance tends to be improved.

Examples of the UV stabilizer include, for example, hindered amine type bis (2,2,6,6-tetramethyl-
4-piperazyl) sebacate, bis (1,2,2,6)
6-pentamethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 1- {2- [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] -2,2,6,6-tetramethylbiperidine The use of 0.05 to 3% by weight may improve the hue stability and weather resistance.

Examples of the antioxidant include 2,4-
Bis (n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine, pentaerystyryl-tetrakis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate, 2,2-thio-bis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5
-Di-t-butyl-4-hydroxy-hydrocinnamamide) and other hindered phenolic compounds, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, trisnonyl When 0.1 to 2% by weight of an antioxidant represented by a phosphoric acid ester compound such as phosphite or tris (2-ethylhexyl) phosphite is used in combination, the heat-melting heat stability tends to be further improved. To be

The hot melt pressure sensitive adhesive composition of the present invention comprises 1
A melt coating viscosity of 20 to 190 ° C., preferably 100
0-50,000 centipoise, more preferably 1,5
The range is from 00 to 30,000 centipoise. 1,0
If it is less than 00 centipoise, it is 10 from the viewpoint of coating workability.
This is because it is difficult to apply one step of 0 to 500 μm.
This is because if it exceeds 10,000 centipoise, the coating workability such as stringiness and lack of uniform thickness becomes a problem.

The fact that the hot-melt pressure-sensitive adhesive composition has an appropriate melt-viscosity behavior and a softening point temperature limitation makes it possible to obtain a good coating productivity during heating, and the solidification rate of the active coating material can be matched so that the hot-coating material can be heated at high speed. This is because there is an advantage that it can be melt-coated, and the rat complementarity, which is important as an adhesive property of the coated product, is sufficiently exhibited.

The kettle for producing the composition of the present invention is not particularly limited, and may be produced by using a set of known polymerization equipment such as a radical polymerization kettle, and the polymerization reaction can be carried out smoothly under heating in a nitrogen stream. A well-known manufacturing pot or the like that can be carried out in the above and is easy to mix and melt can be preferably used.

In the present invention, at least the styrene-based monomer of at least 5 is used as the method for producing the hot-melt pressure-sensitive adhesive composition which satisfies the object of the present invention most inexpensively and sufficiently.
A styrene-based vinyl monomer consisting of 0% by weight or more and one or more of acrylic acid ester and / or methacrylic acid ester monomers is heated to 60 to 150 ° C. to have a polymerization rate of 30 to 90% by weight. Bulk polymerization was carried out, then a plasticizer and a polymerization initiator were added, and solution polymerization was carried out within the same temperature range to complete the polymerization reaction. Finally, the number average molecular weight (Mn) was 2,000 to 15,000, The Z average molecular weight (Mz) is 300,000 or more, and the ratio Mz / Mn of the Z average molecular weight to the number average molecular weight is 50 to 600, preferably 5
A plasticizer-containing composition of a mixed poly (styrene-acryl) resin of a high molecular weight polymer of 0 to 350 and a low molecular weight polymer, and the necessary amount of the thixotropic agent is 120 to 1 in the system.
The most preferable embodiment is the production method of producing the hot-melt pressure-sensitive adhesive composition of the present invention by melt mixing at a temperature of 80 ° C.

Further, in the present invention, the other method for producing the hot-melt pressure-sensitive adhesive composition which satisfies the object of the present invention most inexpensively and sufficiently is at least 50% by weight or more of the styrene monomer. And 160 to 2 styrene-based vinyl monomers consisting of one or more of acrylic acid ester and / or methacrylic acid ester monomers.
A low molecular weight polymer having a number average molecular weight of 2,000 to 8,000 obtained by performing solution polymerization in the presence of a plasticizer was prepared by heating to 30 ° C., and separately, at least 50 weight% of a styrene monomer was prepared. % Or more and one or more acrylate and / or methacrylic acid ester monomers are heated to 60 to 150 ° C., and the polymerization rate is 80 to 90% by weight. Bulk polymerization is performed, and then 0.01 to 1 in a ratio of all monomers.
A number average molecular weight (Mn) obtained by adding divinyl monomer in an amount of% by weight, a plasticizer and a polymerization initiator to complete the polymerization reaction by solution polymerization in the same temperature range is 5,000 to 15,000.
0, Z average molecular weight (Mz) is 400,000 or more, Z
Ratio Mz / Mn of average molecular weight to number average molecular weight is 50 to 60
A heating resin solution of 0 is prepared respectively, and finally the solid content weight ratio of the high molecular weight and the low molecular weight is (30 to 70):
(70 to 30), the mixed resin has a number average molecular weight (Mn) of 2,000 to 15,000, a Z average molecular weight (Mz) of 300,000 or more, and a Z average molecular weight and a number average. A plasticizer-containing resin composition of a mixed poly (styrene-acrylic) resin of a high molecular weight polymer having a molecular weight ratio Mz / Mn of 70 to 350 and a low molecular weight polymer, and further, a necessary amount of a thixotropic agent is 120 to The most preferable method is a production method characterized in that the hot-melt pressure-sensitive adhesive composition of the present invention is finally obtained by melt mixing at a temperature of 180 ° C.

In order to process and manufacture the sticking mat for rat removal, which is the original purpose of the hot-melt pressure-sensitive adhesive composition of the present invention,
The hot melt pressure-sensitive adhesive composition of the present invention is passed through a known hot melt applicator and / or hot melt roll coater to give a hot melt pressure sensitive adhesive composition of 120 to
It is melted at a temperature of 190 ° C., and 50 to 500 μm, preferably 200 to 300 μm on the upper surface of a cardboard substrate prepared in advance.
This can be achieved by producing a pressure-sensitive adhesive mat which is uniformly hot-melt coated over the entire thickness or most of its thickness.

That is, the present invention uses the hot melt pressure-sensitive adhesive composition of the present invention to form 50 to 50 on the upper surface of a cardboard base material.
It includes use such as producing a pressure-sensitive adhesive mat having a thickness of 0 μm, preferably 200 to 300 μm by hot melt coating, and providing the pressure-sensitive adhesive mat for a rat.

Regarding the range of application of the hot melt adhesive composition of the present invention, as described above, it is used as a hot melt adhesive composition for producing a pressure sensitive adhesive mat for rat removal, and other known paper diapers. It may be applied and developed in the fields of adhesives for pressure-sensitive adhesives, pressure-sensitive adhesive tapes, pressure-sensitive labels, temporary fixing materials, etc., and is not particularly limited.

The application method for applying the hot-melt pressure-sensitive adhesive composition of the present invention is not particularly limited, and various known hot-melt applicators may be used. For example, bead-like application, surface-application, Appropriately adopt any known coating method such as dot coating, spray coating, tornado coating, and other special examples such as multiple layer coating processing method and thermal roll transfer coating method. Good.

[0128]

EXAMPLES The present invention will be specifically described below by describing production examples, production comparative examples, examples, and comparative examples of the present invention, respectively, but the present invention is specified or limited only by the production examples and examples. However, the parts or% described in each example mean parts by weight and% by weight, respectively.

The number average molecular weight (M
n) and weight average molecular weight (Mw) and Z average molecular weight (M
z) is the value of Mn, Mw, and Mz obtained by dissolving each polymer in tetrahydrofuran at 0.25% by weight, subjecting the solution to high-speed GPC, and converting from the standard polystyrene elution calibration curve previously obtained by the same method. Was displayed.

Each hot melt type pressure-sensitive adhesive composition (HM composition) prepared in the following Examples and Comparative Examples
Unless otherwise noted, the coating width is 30 cm in advance,
With a reverse type homelt roll coater set at 150 ° C, the coating feed speed is 6 m / min, and the coating is applied once to the decorative coated surface of a 30 cm square, 0.7 mm thick exfoliation-preventing decorative cardboard. The distance between the roll surface and the coated paper surface was adjusted so as to have a thickness of 300 μm, and a homolt coated surface was formed on the entire surface of the decorative paper obtained to prepare a rat trapping mat. The mat was further fitted into the upper surface of the concave portion of a 31 cm square bent-backboard type mount which was separately prepared, and subjected to the established measurement test for gait fixation of the parent mouse.

Weight of 220-
About 250 g of a rat was released, a catching mat was set on the rat walking surface of the cage, the rat was allowed to walk, and the catching state and catching probability at that time were observed.

When the mouse is surely captured and fixed on the adhesive mat in one walk, that is, when the mouse can be captured in a state where it cannot be escaped, it is defined as ◎, and escapes with a probability of 1 to 2 times in 10 walk passages. The probability of catching was identified as ○. If you are walking on the adhesive mat without any resistance
And other than the above was marked as Δ.

Further, in the heat resistance flow test, a release paper was coated with 300 μm at the time of heating and rapidly cooled to obtain an adhesive block body having a size of 5 cm square. The temperature was set at 1 ° C./2 minutes in a dryer capable of raising the temperature at a constant rate, and the melt block placed horizontally was displayed at a temperature at which a flow spread of +3 mm or more was recognized.

Furthermore, the hue stability described in the examples means that the hot melt composition is about 1 in a 200 ml mayonnaise bottle.
The results are shown by observing the degree of color change after melt-inserting 00 parts and leaving it in a hot air dryer at 140 ° C. for 24 hours. Good means that the hue change such as yellow or brown is almost recognized, and bad means that the skin sticking property or the hue change is severe.

Production Example 1 Styrene 60 was used as a monomer in a flask purged with nitrogen.
And 40 parts of n-butyl methacrylate were charged and heated in an oil bath to carry out bulk polymerization reaction at an internal temperature of 130 ° C. for 3 hours. At this time, the polymerization rate of the monomer was 35%.

Next, dioctyl phthalate (DO
After 80 parts of P) was added to bring the internal temperature to 100 ° C., the internal temperature of the initiator liquid consisting of 1 part of azobisisobutyronitrile (AIBN) and 20 parts of DOP was kept constant for 10 hours in advance. While the solution was dropped, the polymerization was continued for 2 hours, resulting in a polymerization rate of 99.8%.

Finally, demonomerization was performed at 100 mmHg at the same temperature to obtain a polymer composition object having a 50% resin content. The polymer obtained at this time was designated as H-1.

It was found that the H-1 form was a high molecular weight product having a non-crosslinked structure which was completely dissolved in tetrahydrofuran.

The molecular weight of the obtained polymer H-1 was measured to find that Mz was 45 × 10 ⁴ and Mw was 19 × 10.
⁴ , Mn is 2.4 × 10 ⁴ , and the Mz / Mn ratio is 19.
0, the Mw / Mn ratio was 7.9. Production Example 2 A polymer composition containing 50% of a plasticizer was obtained in the same manner as in Production Example 1 except that the bulk polymerization rates were 50%, 70% and 90% by extending the reaction time of bulk polymerization. The polymer obtained when the bulk polymerization rate was 50% was H-2, the case where the bulk polymerization rate was 70% was H-3, and the polymer obtained when the bulk polymerization rate was 90% was H-4. showed that. All the polymers were completely compatible with tetrahydrofuran.

Comparative Production Example 1 The reaction time of bulk polymerization was shortened, and the bulk polymerization rate was 20%.
And 1 part azobisisobutyronitrile and 80 xylene
Solution polymerization was completed by adding 1 part of divinylbenzene to 1 part. Otherwise in the same manner as in Production Example 1 above, polymer X
-1 was obtained.

The molecular weight characteristics of polymer X-1 are shown in Table 1.

Comparative Production Example 2 Azobisisobutyronitrile was added to the monomer of Production Example 1 in an amount of 0.
A polymer composition was obtained in the same manner as in Production Example 1, except that 2 parts were added and bulk polymerization was carried out at 100 ° C. for 2 hours.

The polymer obtained at this time was designated as X-2.

It was found that X-2 is a non-crosslinked high molecular weight polymer which completely dissolves in tetrahydrofuran.
The molecular weight characteristics of the obtained polymer X-2 are shown in Table 1.

Production Example 3 After adding 80 parts of DOP of Production Example 1, 0.6 part of divinylbenzene was further added, and otherwise the same as in Production Example 1 to obtain a polymer composition.

The polymer obtained at this time was designated as H-5.

It was found that H-5 is a non-crosslinked high molecular weight polymer which completely dissolves in tetrahydrofuran.
The molecular weight characteristics of the obtained polymer H-5 are shown in Table 1.

Production Example 4 60 parts of styrene and 60 parts of acrylic acid -n- were prepared from the monomer of Production Example 1.
Bulk polymerization was carried out at 130 ° C. for 4 hours in place of butyl 60 parts and methacrylic acid 10 parts to obtain a polymerization rate of 50%. Otherwise in the same manner as in Production Example 1 to obtain a polymer composition.

The polymer obtained at this time was designated as H-6.

It was found that H-6 is a high molecular weight polymer having a non-crosslinked structure which completely dissolves in tetrahydrofuran.
The molecular weight characteristics of the obtained polymer H-6 are shown in Table 1.

Comparative Production Example 3 A polymer composition obtained in the same manner as in Production Example 4 except that methacrylic acid in Production Example 4 was replaced with acrylic acid was an apparent semi-gel-like material.

The polymer obtained at this time was designated as X-3.

It was found that X-3 was a high-molecular weight product having a crosslinked structure without being completely dissolved in tetrahydrofuran. Production Example 5 60 parts of styrene and methacrylic acid-n were used as the monomers of Production Example 1.
-Butyl 22.5 parts, except that the acrylonitrile macromer having a Mw / Mn ratio of 1.3 and a weight average molecular weight Mw of about 2300 was changed to 7.5 parts and the bulk polymerization rate was 40% at an internal temperature of 130 ° C. A polymer composition was obtained in the same manner as in Production Example 1.

The polymer obtained at this time was designated as H-7, was confirmed to be a non-crosslinked polymer which was completely dissolved in tetrahydrofuran, and its molecular weight characteristics are shown in Table 1. Production Example 8 A polymer composition was obtained in the same manner as in Production Example 7 except that the bulk polymerization rate was 70%.

The polymer obtained at this time was designated as H-8, was confirmed to be a non-crosslinked polymer which was completely dissolved in tetrahydrofuran, and its molecular weight characteristics are shown in Table 1. Production Example 9 (Production Example of Low Molecular Weight Polymer) In the same polymerization apparatus as in Production Example 1, xylene or a 1: 1 mixed solvent of xylene and cumene was charged, and 90 parts of styrene and methacrylic acid were added at 155 ° C.
A mixed solution of 10 parts of n-butyl and 3 to 5 parts of azoisobutyronitrile was added dropwise over 5 hours, followed by polymerization for 2 hours, and then depressurization was completed to complete desolvation, and Mn was L-
Each low molecular weight polymer of 1 and L-2 was obtained. The molecular weight characteristics are shown in Table 1. Comparative Production Example 3 (Low molecular weight polymer production example) In the same polymerization apparatus as in Production Example 1, xylene or a 1: 1 mixed solvent of xylene and cumene was charged and 90 parts of styrene and methacrylic acid-n were added at 155 ° C.
A mixed solution of 10 parts of butyl and 1 part of azoisobutyronitrile was added dropwise over 5 hours, followed by polymerization for 2 hours, and then depressurization was completed to complete desolvation, and Mn was compared with L-3 below. A low molecular weight polymer was obtained. The molecular weight characteristics are shown in Table 1.

The measurement results of the molecular weight of the thermoplastic styrene-acrylic resin in the HM composition (average molecular weight of mixed resin of high molecular weight and low molecular weight) are shown in each table as the molecular weight of the mixed base resin. Example 1 The H-1 polymer obtained in Production Example 1 was added to a 100 ° C. heating system after production so that each component (Production Example 9 was used) so that the compounding ratio was as shown in Table A.
The powder of the low molecular weight product obtained in 1., a plasticizer, and a thixotropic agent) were added, and the mixture was melt-mixed at the same temperature, and then taken out into a mold release box, and the HM composition No. 1-No. 3 was obtained.

The measurement results of the base resin molecular weight of each HM composition are shown in Table 2 together. Example 2 Each of the (H-2) to (H-5) polymers obtained in Production Example 2 to Production Example 5 was added to a 100 ° C. heating system after production so that the compounding ratio was as shown in Table-B. The components (low molecular weight powder obtained in Production Example 9, plasticizer, and thixotropic agent) were added, melt-mixed at the same temperature, and then taken out in a mold release box to obtain HM composition No. 4 to No. Got 7.

Composition No. 4 to No. Finally, the product name “IRGANOX 101
0% "and 0.02% of bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate
Were respectively contained.

The measurement results of the base resin molecular weight of each HM composition are also shown in Table 3. Example 3 Each of the (H-6) to (H-8) polymers obtained in Production Examples 6 to 8 was added to a 120 ° C. heating system after production so that the compounding ratio was as shown in Table-C. Each component [low molecular weight powder obtained in Production Example 9, a plasticizer, a thixotropic agent, and, if necessary, a tackifier resin (however, in Table C, the tackifier resin is simply referred to as TF). Arakawa Chemical Co., Ltd .: transparent trogin ester SE-311], and melt-mixed at the same temperature, and then taken out into a mold release box, respectively. 8
~ No. I got 11.

Composition No. 8 to No. 11 is the product name “Irganox 107” as an antiaging agent.
6 "as well as 0.02% of bis (2,2,6,6-tetramethyl-4-piperazyl) sebacate.

Table 4 also shows the measurement results of the base resin molecular weight of each HM composition. Example 4 Styrene 60 as a monomer in a nitrogen purged flask
And 40 parts of n-butyl methacrylate were charged and heated in an oil bath to carry out bulk polymerization reaction at an internal temperature of 130 ° C. for 3 hours. At this time, the polymerization rate of the monomer was 35%.

Next, 80 parts of xylene was added to the same system to bring the internal temperature to 100 ° C., and then an initiator solution consisting of 1 part of azobisisobutyronitrile (AIBN) and 40 parts of xylene was preheated to the internal temperature over 10 hours. Was added dropwise while maintaining constant, and the polymerization was continued for another 2 hours. As a result, the polymerization rate was 99.8%. 100 parts of the low-molecular-weight substance L-1 previously produced in Production Example 9 was added to the same polymerization-terminated system and uniformly dissolved.

Finally, the solvent was removed at 100 mmHg at the same temperature to obtain a mixed polymer Y-1. It was found that the mixed polymer of Y-1 was a non-crosslinked high molecular weight polymer which was completely dissolved in tetrahydrofuran.

The average molecular weight of the obtained polymer Y-1 was measured and found to be Mz of 45.2 × 10 ⁴ , Mw of 9.8 × 10 ⁴ , and Mn of 0.69 × 10 ⁴ . , Mz /
The Mn ratio was 65.5, and the Mw / Mn ratio was 14.2.

Y-1 which is solid at room temperature is pulverized to have a particle size of 3 mm or less, and 100 parts of the powder is mixed with 10 parts of carbon black as a colorant, 3 parts of polypropylene wax, and spirone as a charge control agent. Black TRH0.
5 parts were melt-kneaded with a twin-screw extruder at 140 to 150 ° C.,
A homelt type composition DY-1 which can be used as an electrophotographic toner powder having a particle diameter of 8 to 20 μm was prepared through the steps of cooling and solidification, pulverization, classification, and colloidal silica treatment.

The DY-1 toner powder has a blow charge amount of -1.
It was 5 μC / g, and its suitability for fixing toner at 180 ° C. on ordinary copy paper and excellent offset property was found, and its practicality as an electrophotographic toner was fully recognized.

Next, 100 parts of DY-1 toner powder and 80 parts of dibutyl phthalate were charged into a flask and the temperature was 100 ° C. for 1 hour.
Was heated to sufficiently dissolve the components soluble in the toner resin.
Then, it was subjected to a pressure filtration treatment using a 300-mesh cloth under heating to obtain a black adhesive resin containing 8% of carbon black.

Further, 2 parts of 12-hydroxystearic acid was added to the system, and the mixture was heated, mixed and dissolved to finally obtain a black homelt-type pressure-sensitive adhesive composition DY-1A.

The melt viscosity of DY-1A at 160 ° C. is the same as that of No. B Brookfield viscometer. It was a hot melt composition having a low viscosity of 27 to 32 ps as measured by a 24 rotor. DY-1A was applied to the whole surface of one side with a hot melt roll coater having a roll surface temperature of 130 to 135 ° C. on a decorative board having a thickness of 20 × 30 cm and a thickness of 0.7 mm so that the coating thickness would be 200 μ. An adhesive mat for a small animal trap having a pole tack force of 32/32 in an atmosphere of 20 ° C. was prepared.

As a result of walking a parental mouse having a weight of about 200 g on the mat in a freely walking state, the mouse was immediately captured and fixed on the mat in the first walk, and the mouse could not escape from the mat until the next day. I was there.

Comparative Example 1 Each of the polymers of H-1, H-2, and H-8 obtained in Production Example was added to the heating system at 100 ° C. after production so that each component had the compounding ratio shown in Table D. (Low-molecular-weight substance L-3 obtained in Comparative Production Example 3, plasticizer, thixotropic agent) were added, and melt-mixed at the same temperature, and then taken out in a mold release box to obtain HM composition No. 12
~ No. I got 16.

The measurement results of the base resin molecular weight of each HM composition are shown in Table 5 together.

[0173]

[Table 1]

[0174]

[Table 2]

[0175]

[Table 3]

[0176]

[Table 4]

[0177]

[Table 5] Explanation of symbols described in Tables 2 to 5: DOP; abbreviation of dioctyl phthalate DBP; abbreviation of dibutyl phthalate for rodent trapping ability; ⊚: 30 cm, 300 μm thick on one side of each 0.7 mm thick decorative cardboard A weight of 20 is applied to each of the melt coated surfaces of the 10 traps having the homelt coated surface.
It means that all 10 mice of 0 ± 20 gr could be fixed and captured. ◯: 30 cm, each side of 0.7 mm thick cardboard was formed with a 300 μm thick homolt coated surface. The weight of each of the 10 traps was 20
It means that 8 to 9 mice could be fixed and captured when 10 mice of 0 ± 20 gr were passed through.] Applicability for coating work: ◎: For surface coating using a gear pump type die coater at 135 ° C. In this case, when the threading property during ON / OFF is not observed, the predetermined film thickness can be secured at one time, and uniform coating is possible. 12-hydroxySt acid; an abbreviation for 12-hydroxystearic acid. Reagent-1; N-lauryl-L-glutamic acid-α, γ-
Di-n-butyramide. Reagent-2; N-lauryl-L-aspartic acid-α, γ
-Di-n-butyramide. Reagent-3; N-stearyl-L-glutamic acid-α, γ
-Di-n-butyramide. Reagent-4; N-stearyl-L-aspartic acid-α,
γ-di-n-butyramide. Reagent-5; N-lauryl-L-glutamic acid-α, γ-
Di-n-hexylamide. T. F: Abbreviation for tackifier. Large liquid dripping property; severe liquid dripping flow property was observed at 40 ° C. Comparative Example 2 Composition No. 3 in Table 5 of Comparative Example 1 12 and No. 16
For each 100 parts of each composition, about 30 to 50 parts of dioctyl phthalate was additionally added and melted so that the temperature could be increased to 30/32 with a ball tack at an atmosphere of 20 ° C. and a coating thickness of 200 μm. Both compositions showed remarkable dripping property in an atmosphere of 50 ° C., the coating film thickness could not be secured at a high temperature place on the coated mat surface, and flowed around the mat installation area, causing severe contamination. It was found that the adhesive mat was difficult to collect, and the heat-resistant cohesive force was extremely insufficient.

[0178]

EFFECTS OF THE INVENTION The hot-melt pressure-sensitive adhesive compositions shown in Comparative Examples have extremely low tackiness or weak tackiness, and particularly have poor finger-touch tackiness, and lack in suitability for capturing matrice on sticky mats. It was the result. This result was presumed to be the result that the molecular weight of the styrene-acrylic resin and its distribution greatly influence each other.

As is clear from Comparative Example 2, when a plasticizer of the same type was further added to the composition of Comparative Example 1, the tackiness was improved, but an important characteristic was the heat resistance at 50 ° C. It is also known that the flowability cannot be secured.

On the other hand, in each of the hot-melt pressure-sensitive adhesive compositions of Examples 1 to 11 and DY-1A, the flow initiation temperature was 50 ° C. or higher, which had good heat-resistant cohesive strength characteristics, and was excellent in the present invention. It was the purpose and again the following was found. Of the so-called acryl-styrene toner base resins that are generally accepted as electrophotographic toner resins, at least 50% by weight and at most 50% by weight or less of styrene monomer. Which has a molecular weight distribution of 2 peaks or more, and which has a number average molecular weight (Mn) of 2,
000 to 15,000, Z average molecular weight (Mz) is 30
50,000 or more, ratio of Z-average molecular weight to number-average molecular weight (M
z / Mn) is 50 to 600 and the glass transition temperature is 50 to 1
Polystyrene was added to 100 parts by weight of the thermoplastic styrene-acrylic resin at 20 ° C. and / or 100 parts by weight of the thermoplastic styrene-acrylic resin recovered after being used as a so-called electrophotographic toner recovered from waste printed paper. 0.01-150 parts by weight of a plasticizer capable of plasticizing and 0.01 of a thixotropic agent comprising one of the above-mentioned (A) to (C).
The composition of the hot-melt type pressure-sensitive adhesive composition obtained by melt-mixing 5 to 5 parts by weight with low odor and rich hue stability, which is the object of the present invention, can be preferably applied to an inexpensive pressure-sensitive adhesive mat for rat collecting. It turned out to be a thing.

As is clear from the above results, the styrene-acrylic base resin for electrophotographic toner which is currently available on the market at low cost is a strong adhesion type mouse whose main purpose is to capture small animals such as mice and smaller animals. It was unexpectedly found that it is possible to provide a hot melt composition for harvesting.

That is, it is considered that the technique for opening up a new method of recycling the toner recovery resin has been established as a technique useful and important for social life.

Claims (14)

[Claims] 1. Obtained by copolymerizing a styrenic vinyl monomer containing at least 50% by weight and at most 50% by weight or less of a styrene-based monomer with an acrylic ester and / or a methacrylic ester. It has a molecular weight distribution above the peak, and its number average molecular weight (Mn) is 2,0.
00 to 15,000, Z average molecular weight (Mz) is 300,
000 or more, the ratio of the Z average molecular weight to the number average molecular weight (Mz /
Mn) 50-600, glass transition temperature 50-120
Styrene to 100 parts by weight of the thermoplastic styrene-acrylic resin composition and / or 100 parts by weight of the thermoplastic styrene-acrylic resin composition recovered from waste printed paper after being used as a toner for electrophotography. 10 to 150 parts by weight of possible plasticizers and the following (A) to (C)
A hot-melt pressure-sensitive adhesive composition obtained by melt-mixing with 0.01 to 5 parts by weight of at least one thixotropic agent selected from the group consisting of: (A) a hydroxy higher fatty acid compound having an integer of 12 to 30 carbon atoms, (B) a slack resin,
And (C) N-lauryl-L-glutamic acid-α, γ
-Di-n-butylamide, N-lauryl-L-aspartic acid-α, γ-di-n-butylamide, N-stearyl-L-glutamic acid-α, γ-di-n-butylamide, N-stearyl-L- One or a mixture of two or more selected from aspartic acid-α, γ-di-n-butylamide and N-lauryl-L-glutamic acid-α, γ-di-n-hexylamide. 2. A thermoplastic styrene-acrylic resin composition comprising a styrene-based vinyl monomer containing at least 50% by weight and at most 50% by weight or less of a styrene-based monomer, an acrylic ester and / or a methacrylic ester. Polymerization is carried out by bulk polymerization up to a polymerization rate of 30 to 90% by weight, and then a plasticizer capable of plasticizing polystyrene and 0.01 to 1% by weight of a divinyl compound in the total charged monomers and initiation of polymerization. The number average molecular weight Mn obtained by separately polymerizing the styrene-based vinyl monomer by the solution polymerization method is 1 and the high molecular weight polymer obtained by completing the solution polymerization by further adding the agent and lowering the viscosity. 2. A hot melt type viscous resin according to claim 1, which is a mixed resin composition with a low molecular weight polymer of 1,000 to 5,000, wherein the resin composition is prepared for non-toner use. Glue composition. 3. A thermoplastic styrene-acrylic resin composition comprising at least 50% by weight and at most 49.9% by weight or less of styrene-based monomers, and further 0.1 or less acrylic acid ester and / or methacrylic acid ester. A styrene-based vinyl monomer containing 10 to 10% by weight of methacrylic acid by bulk polymerization up to a polymerization rate of 30 to 70% by weight, and then a plasticizer and a solvent capable of plasticizing polystyrene;
A high-molecular weight polymer obtained by completing the solution polymerization by additionally adding a divinyl compound in an amount of 0.01 to 1% by weight based on the total charged monomers and a polymerization initiator to further reduce the viscosity, It is a mixed resin composition with a low molecular weight polymer having a number average molecular weight Mn of 1,000 to 5,000 obtained by separately polymerizing the styrene vinyl monomer by a solution polymerization method, and the resin composition is The hot-melt pressure-sensitive adhesive composition according to claim 1, which is prepared for non-toner use. 4. The thermoplastic styrene-acrylic resin composition comprises styrene and / or α-methylstyrene of 60 to 60%.
95% by weight, having a radically polymerizable unsaturated bond group at one end and having a ratio Mw / Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2 or less and a weight average molecular weight (Mw) of 1,000. 0.5 to 20% by weight of acrylonitrile macromer having a polyacrylonitrile segment in the range of ˜30,000, 4.5 to 39.5% by weight of (meth) acrylic acid ester, and 0 to 10% by weight of methacrylic acid. Styrene-based vinyl monomer containing and is subjected to bulk polymerization at a polymerization rate of 30 to 70% by weight, and then a plasticizer or solvent capable of plasticizing polystyrene, a polymerization initiator, and methacrylic acid are styrene-based vinyl monomers. Only when it is not present in the monomer, 0.01 to 1% by weight of the divinyl compound in the total amount of the charged monomers is additionally added to lower the viscosity of the system. , A high molecular weight polymer obtained by complete solution polymerization, is independently a number average molecular weight Mn obtained by polymerizing the styrene-based vinyl monomer in solution polymerization, 000
The hot melt adhesive composition according to claim 1, which is a mixed resin composition with a low molecular weight polymer of 5,000. 5. The thermoplastic styrene-acrylic resin composition comprises 49.5 to 89.5% by weight of a styrene-based monomer,
It has a radically polymerizable unsaturated bond group at one end and has a ratio Mw / Mn of weight average molecular weight (Mw) and number average molecular weight (Mn) of 2
And the weight average molecular weight (Mw) is 1,000 to 1
0.5-20% by weight of polystyrene macromer having polystyrene segments in the range of 5,000, 4.4-40% by weight of (meth) acrylic acid ester, and 0.1-10% by weight of methacrylic acid. The styrene-based vinyl monomer containing is polymerized by bulk polymerization up to a polymerization rate of 30 to 70% by weight, and then a plasticizer or a solvent capable of plasticizing polystyrene and a proportion of 0.0 in the total charged monomers.
A high molecular weight polymer obtained by additionally adding 1 to 1% by weight of a divinyl compound and a polymerization initiator to lower the viscosity of the system and completing the solution polymerization, and the styrene-based vinyl monomer are separately dissolved in a solution. The number average molecular weight Mn obtained by polymerization by the polymerization method is 1,000.
2. A hot melt pressure-sensitive adhesive composition according to claim 1, which is a mixed resin composition with a low molecular weight polymer of from about 5,000 to about 5,000, wherein the resin composition comprises a non-toner resin. 6. A thermoplastic styrene-acrylic resin composition is melt-mixed in a range of 1 to 20 parts by weight with respect to 100 parts by weight of the colorant, and provided as an electrophotographic toner.
The hot-melt pressure-sensitive adhesive composition according to claim 1, which is a styrene-acrylic resin recovery composition separated and recovered from the printed waste paper. 7. The thermoplastic styrene-acrylic resin composition is a mixed resin composition containing a high molecular weight polymer and a low molecular weight polymer, and the high molecular weight polymer has a styrene vinyl monomer polymerization rate of 30. Up to 70% by weight is carried out by bulk polymerization, then a plasticizer capable of plasticizing polystyrene and a polymerization initiator are additionally added to lower the viscosity to complete the solution polymerization, and the high molecular weight product: low. The hot-melt pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the mixing ratio of the molecular weight is (30 to 90) :( 70 to 10) in terms of solid content weight ratio. 8. The number average molecular weight Mn of the low molecular weight polymer is 1,000 to 5,000.
Hot-melt adhesive composition of. 9. The plasticizer is one kind or two or more kinds selected from adipic acid dialkyl ester, azelaic acid dialkyl ester, and phthalic acid dialkyl ester, according to any one of claims 1 to 8. Hot melt adhesive composition. 10. The plasticizer is selected from adipic acid-dioctyl, adipic acid-dinonyl, adipic acid-ditridecyl, azelaic acid-dioctyl, phthalic acid-di-n-butyl, phthalic acid-dioctyl, and phthalic acid-dinonyl. The hot melt pressure-sensitive adhesive composition according to claim 9, which is one kind. 11. The hot melt type pressure-sensitive adhesive composition according to claim 1, wherein the thixotropic agent is 12-hydroxystearic acid. 12. A hot-melt pressure-sensitive adhesive composition further comprising at least one selected from the group consisting of hydrogenated terpene resin, hydrogenated rosin, hydrogenated rosin ester derivative and polymerized rosin as a tackifier. The hot-melt pressure-sensitive adhesive according to any one of claims 1 to 11, characterized in that when it is contained in the range of 1 to 30% by weight and applied to an olefin material other than paper, the adhesion to a substrate is improved. Composition. 13. At least 50-styrene-based monomer.
95% by weight and one or more of acrylic acid ester and / or methacrylic acid ester 4.9 to 4
9.9% by weight and 0.1-10% by weight of methacrylic acid
A styrene-based vinyl monomer containing
A plasticizer which can be bulk polymerized to a polymerization rate of 30 to 70 wt% by heating to ℃ and then plasticize polystyrene.
A mercaptan chain transfer agent, a polymerization initiator, and if necessary, a solvent is further added to complete the polymerization reaction by solution polymerization in the same temperature range, and when a solvent is used, the solvent is removed to remove the high molecular weight polymer and the low molecular weight. A polymer mixture was prepared, and the high molecular weight polymer and the low molecular weight polymer were mixed in a solid content weight ratio of (30 to 90) :( 7
0-10), and the number average molecular weight (Mn) of the mixed resin is 5,000 to 15,000 and the Z average molecular weight (Mz) is 3
Thermoplastic styrene having a Mz / Mn ratio of not less than 0,000 and a Z-average molecular weight and a number-average molecular weight of 50 to 600
10 to 150 parts by weight of a plasticizer capable of plasticizing polystyrene and 0.01 to 5 parts by weight of a thixotropic agent are produced based on 100 parts by weight of the plastic styrene-acrylic resin content. 120-1 to include
A method for producing a hot-melt pressure-sensitive adhesive composition, which comprises melt-mixing at a temperature of 80 ° C. 14. A rat, characterized in that the hot-melt pressure-sensitive adhesive composition according to claim 1 or 15 is hot-melted and hot-melt coated on one surface of a cardboard base material to a thickness of 50 to 500 μm. Adhesive mat for removal.