JP2948495B2 - Hot melt resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot melt resin composition having excellent hot melt workability and heat resistance.

[0002]

2. Description of the Related Art Hot-melt resins are superior to solvent-type resins and emulsion-type resins in terms of working environment, air pollution, danger of fire, unnecessary drying process, energy saving, etc. Has been proposed. However, due to its properties, hot melt resins have relatively low heat resistance and are limited in the usable temperature range. Therefore, various proposals have been made to improve the heat resistance (hot strength) of the hot melt resin composition.

[0003] JP-A-50-139135 and JP-A-51-19035 describe hot melt resin compositions in which an acrylic polymer having a carboxyl group is crosslinked with metal ions. JP-A-56-
No. 14573 describes a hot melt resin composition containing a crosslinked polymer obtained by adding maleic anhydride to low molecular weight polyisoprene and crosslinking with metal ions, and a tackifier.

JP-A-58-125774 discloses an acrylic polymer having a carboxyl group, a metal salt and o-
A hot melt resin composition comprising methoxyaryl acid is described. JP-A-5-202345 discloses that
A hot melt resin composition comprising an acrylic polymer having a carboxyl group neutralized by a polyvalent metal is described.

[0005] These conventional hot melt resin compositions are:
Improvement of heat resistance is hot melt workability (fluidity during heating)
And the balance between heat resistance and hot melt workability is poor. JP-A-56-161484 describes a hot melt resin composition containing a graft polymer or a block polymer obtained by polymerizing a monomer that gives another polymer in the presence of a polymer.

JP-A-56-59882 discloses a hot-melt resin composition containing a graft polymer obtained by reacting functional groups of two polymers having functional groups and having different compositions with each other. Have been. JP-A-58-53969
Japanese Patent Application Publication No. JP-A-2002-110139 describes a hot melt resin composition containing a polymer having a branched structure, which is obtained by polymerizing a monomer that gives another polymer in the presence of a polymer.

JP-A-58-61160 describes a hot melt resin composition containing a mixture obtained by heating and mixing two kinds of polymers having different compositions in the presence of a peroxide. JP-A-2-103277 and JP-A-5-3
No. 1595 describes a hot melt resin composition containing a star-shaped polymer having the same block polymer portion extending from the same center.

Japanese Unexamined Patent Publication (Kokai) No. 2-167380 discloses a hot melt resin composition containing a gflat polymer obtained by copolymerizing a macromonomer and a low molecular weight monomer. These block polymer and graft polymer,
Although it has relatively good hot melt workability, it has poor heat resistance. On the other hand, a hot-melt resin composition in which a moisture-curable functional group such as an isocyanate group is introduced has been proposed in order to perform a crosslinking reaction after the hot-melt operation and to improve heat resistance. This hot melt resin composition requires a long time to exhibit heat resistance, and there is a concern that performance may change over time.

Further, a hot melt resin composition which is cured by irradiation with energy rays such as ultraviolet rays and electron beams has been proposed. This hot melt resin composition contains a solvent or a dispersion medium, and requires equipment and energy for irradiating energy rays. Therefore, two characteristics of the hot melt resin, that is, no drying step and energy saving, are impaired.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which has excellent heat resistance and hot melt workability, and requires less time than the conventionally known moisture-curable and energy ray irradiable cross-linkable hot melt resin compositions. The object of the present invention is to provide a hot-melt resin composition which can exhibit the same or almost the same heat resistance with equipment and energy, and hardly cause a change in performance with time such as weather resistance.

[0011]

According to a first aspect of the present invention, there is provided a hot melt resin composition comprising a polyvalent mercaptan or a polyvalent mercaptan.
And the rest of the mercapto group protons dissociated
Includes thermoplastic addition polymers having certain polyvalent mercaptan moieties and multiple polymer moieties. The thermoplastic addition polymer is
It has a number average molecular weight of 10,000 to 200,000.
The plurality of polymer moieties extend radially from the polyvalent mercaptan portion, and a carbon atom at one end thereof is a polyvalent mercaptan.
The structure attached to the sulfur atom derived from the partial mercapto group
With two or more different compositions.

The hot melt resin composition of the present invention comprises a second
According to the aspect, in the first aspect, the plurality of polymer portions further have a composition in which the compositions of the polymer portions change with a gradient composition . The hot melt resin composition of the present invention,
According to a third aspect, it comprises a thermoplastic addition polymer. The thermoplastic addition polymer has a number average molecular weight of 10,000 to 200,000, has only one glass transition temperature peak having a width of 50 ° C. or more, and has a parallel light transmittance of 85% or more.

[0013] The hot melt resin composition of the present invention comprises
According to the embodiment, in any one of the first embodiment to the third embodiment, the thermoplastic addition polymer is formed from a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. It is configured. According to a fifth aspect, the hot melt resin composition of the present invention includes a thermoplastic addition polymer obtained by a production method including a preparation step, an addition step, and a polymerization step. The preparing step is a step of preparing a mixture containing the first polymerizable unsaturated monomer and the polyvalent mercaptan. The adding step involves adding the first mixture to the prepared mixture.
This is a step of adding a second polymerizable unsaturated monomer having a composition different from that of the above polymerizable unsaturated monomer. The polymerization step is a step of performing radical polymerization of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer starting from the mercapto group of the polyvalent mercaptan.

[0014] According to a sixth aspect of the hot melt resin composition of the present invention, in the fifth aspect, the production method comprises the steps of: The method further includes a pre-polymerization step of performing radical polymerization of the polymerizable unsaturated monomer. According to a seventh aspect, the hot melt resin composition of the present invention contains a branched (star-shaped) thermoplastic addition polymer obtained by a production method including a preparation step and a polymerization step. The preparation step is a step of preparing a mixture containing a polymerizable unsaturated monomer comprising a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer and a polyvalent mercaptan. The polymerization step is a step of performing radical polymerization of a polymerizable unsaturated monomer starting from a mercapto group of a polyvalent mercaptan.

[0015] The hot melt resin composition of the present invention comprises
According to the aspect, in any one of the first aspect to the seventh aspect, a metal ion source is further included. According to a ninth aspect, the hot melt resin composition of the present invention, in the eighth aspect, further comprises a phosphate ester. According to the tenth aspect, the hot melt resin composition of the present invention has a (meth) acrylic thermoplastic resin containing a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. It contains a polymer, a metal ion source, and a phosphate.

The hot melt resin composition of the present invention comprises
According to one embodiment, in any one of the first embodiment to the tenth embodiment, a tackifier resin is further included. According to the twelfth aspect, the hot melt resin composition of the present invention
In any of the first to eleventh aspects,
It further contains a wax.

[0017]

According to the first aspect, the hot melt resin composition of the present invention comprises a polyvalent mercaptan portion, and a plurality of polymer portions having two or more different compositions extending radially from the polyvalent mercaptan portion. With 10,000 to 200,
By including a thermoplastic addition polymer having a number average molecular weight of 000, a plurality of polymer parts have a branched structure (star-shaped block structure) extending radially from a polyvalent mercaptan part. Linear polymer of
Compared with the block polymer / graft polymer, the viscosity becomes lower at the time of hot melt, and the workability is good. It has a larger cohesive force than the polymer for melt resin, and thus has excellent heat resistance.

The hot melt resin composition of the present invention comprises a second
According to the first aspect, in the first aspect, the plurality of polymer portions further have a composition that continuously changes throughout the aggregate of the thermoplastic addition polymer, whereby the thermoplastic addition polymer has a gradient. Because of having a star block structure of the composition, the intermolecular entanglement is larger at the use temperature and the cohesive force is larger than that of a conventionally known polymer for a hot melt resin. Have.

The hot-melt resin composition of the present invention has a third
According to the embodiment, a thermoplastic resin having a number average molecular weight of 10,000 to 200,000, having only one glass transition temperature peak having a width of 50 ° C. or more, and having a parallel light transmittance of 85% or more is provided. By containing a polymer, compared to a linear polymer, block polymer, or graft polymer having the same molecular weight, the viscosity becomes lower at the time of hot melt, workability is better, and the intermolecular entanglement is larger at the use temperature. It has a larger cohesive force than the polymer for hot melt resin, and therefore has excellent heat resistance and is transparent.

The hot-melt resin composition of the present invention comprises
According to the aspect, in any one of the first aspect to the third aspect, the thermoplastic addition polymer may contain a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. Is a (meth) acrylic resin having a carboxyl group, so that any one of the hot melt resin compositions according to the first to third aspects has a molecular weight at a use temperature. It has the further advantage that the entanglement is greater and the heat resistance is better and the weather resistance is better.

The hot-melt resin composition of the present invention comprises
According to the aspect, the preparing step of preparing a mixture containing the first polymerizable unsaturated monomer and the polyvalent mercaptan, and the prepared mixture is different from the first polymerizable unsaturated monomer. An adding step of adding a second polymerizable unsaturated monomer having a composition, and a first step starting from a mercapto group of a polyvalent mercaptan.
A radical polymerization of a mixture of the polymerizable unsaturated monomer and the added second polymerizable unsaturated monomer, and a thermoplastic addition polymer obtained by a production method. Since the thermoplastic addition polymer has a star-shaped block structure, it has a lower viscosity at the time of hot melt than a linear polymer / block polymer / graft polymer having the same molecular weight, and has good workability and operating temperature. It has a large cohesion between molecules and a larger cohesive force than conventionally known polymers for hot melt resins, and thus has excellent heat resistance. In particular, when radical polymerization is performed while gradually adding the second polymerizable unsaturated monomer, the thermoplastic addition polymer has a gradient composition, and thus has the advantage of being more excellent in heat resistance and being transparent. Have.

[0022] The hot melt resin composition of the present invention comprises
According to the aspect, in the fifth aspect, the production method performs radical polymerization of the first polymerizable unsaturated monomer starting from the mercapto group of the polyvalent mercaptan between the preparation step and the addition step. By further including a prepolymerization step, there is an additional advantage that both heat resistance and hot melt workability can be easily achieved.

The hot-melt resin composition of the present invention comprises
According to the embodiment, a preparation step of preparing a mixture containing a polymerizable unsaturated monomer composed of a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer and a polyvalent mercaptan, And a polymerization step of radically polymerizing a polymerizable unsaturated monomer starting from the mercapto group of a polyvalent mercaptan, thereby obtaining a thermoplastic addition polymer having a branched structure. Has a star-shaped structure, so it has a lower viscosity during hot melt than a linear polymer of the same molecular weight, and has good workability. Since it is a (meth) acrylate resin, it has excellent weather resistance and is transparent.

[0024] The hot melt resin composition of the present invention comprises
According to the aspect, in any one of the first aspect to the seventh aspect, when the thermoplastic addition polymer further includes a metal ion source, the thermoplastic addition polymer is cross-linked with metal ions, so that the cohesive force at the use temperature is reduced. This has the further advantage that the balance becomes larger and the balance between the cohesive force and the hot melt viscosity is improved.

[0025] The hot melt resin composition of the present invention comprises
According to the aspect, in the eighth aspect, when a phosphate ester is further contained, the phosphate ester coordinates to the metal ion, so that the bonding force between the carboxyl group and the metal ion decreases, and the hot melt viscosity decreases. In addition, there is an advantage that workability is improved. According to a tenth aspect, the hot melt resin composition of the present invention has a (meth) acrylic thermoplastic resin containing a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. By containing the polymer, the metal ion source, and the phosphate, the thermoplastic addition polymer is cross-linked by the metal ion, so that the cohesive force becomes larger, and further, the phosphate is coordinated with the metal ion. Therefore, the bonding force between the carboxyl group and the metal ion is reduced, the viscosity of the hot melt is reduced, and the workability is improved.

The hot melt resin composition of the present invention comprises
According to one embodiment, in any one of the first embodiment to the tenth embodiment, by further including a tackifying resin, the hot melt viscosity can be reduced, the cohesive force can be increased, and the tackiness can be improved. Is further improved. According to the twelfth aspect, the hot melt resin composition of the present invention has an advantage that, in any one of the first aspect to the eleventh aspect, by further including a wax, the hot melt viscosity becomes lower. Have more.

[0027]

[Explanation of means]

[Hot Melt Resin Composition According to First Embodiment] The hot melt resin composition of the present invention, according to the first embodiment, comprises a thermoplastic addition polymer having a polyvalent mercaptan portion and a plurality of polymer portions. Including. The number average molecular weight of the thermoplastic addition polymer is from 10,000 to 200,000. When the number average molecular weight is less than the above range, heat resistance is insufficient and cohesive strength (holding force) during use is reduced. When the number average molecular weight exceeds the above range, the hot melt viscosity is high and the handling property is poor. In consideration of the balance that the heat resistance is sufficiently high and the hot melt viscosity is sufficiently low, the number average molecular weight of the thermoplastic addition polymer is preferably from 50,000 to 15
It is 0000.

The thermoplastic addition polymer has a molecular weight distribution (Mw
/ Mn) 4 or less. 4 molecular weight distribution
If it is larger than the above, the hot melt viscosity may be high and the workability may be deteriorated when there are many high molecular weight components, and the heat resistance may be low when there are many low molecular weight components. The polyvalent mercaptan portion refers to a remaining portion in which protons of a plurality of mercapto groups have been dissociated from a polyvalent mercaptan (a mercaptan having two or more mercapto groups) described in a fifth embodiment described later.

The polyvalent mercaptan moiety is preferably a 3-6 functional mercaptan described in the fifth embodiment,
More preferably, it is a remaining portion in which protons of a plurality of mercapto groups are dissociated from the 4- to 6-functional mercaptan described in the fifth embodiment. The reason for this is that the thermoplastic addition polymer has a star-shaped block structure that extends radially from the same center, so that the effect (for example, high cohesion) due to the entanglement between the polymer parts and the morphological change of the phase separation structure are reduced. This is because there is an advantage that it can be expected.

The polymer portion extends radially from the polyvalent mercaptan portion. The polymer portion extending radially from the polyvalent mercaptan portion means that two polymer portions per polymer extend in two directions from the polyvalent mercaptan portion (including a case where the polymer portion extends linearly). And the case where three or more polymer portions extend from the polyvalent mercaptan portion in three or more directions per polymer. A carbon atom at one end of the polymer moiety is attached to a sulfur atom derived from the mercapto group of the polyvalent mercaptan moiety.

The polymer moiety usually has a number average molecular weight
1,000 to 150,000, preferably 3,000 to
100,000. If the number average molecular weight of the polymer portion is below the above range, it may not be possible to introduce properties based on the polymer portion into the thermoplastic addition polymer, and if it exceeds, not only the hot melt viscosity becomes high but also the viscosity during production. And it may be unfavorable in terms of productivity.

The thermoplastic addition polymer has a plurality of polymer portions per polymer. The polymer portion is a portion having a homopolymer or copolymer structure obtained by radical polymerization of a polymerizable unsaturated monomer. The polymer portion obtained by radical polymerization is more diverse in the type of composition than the polymer portion generated by ionic polymerization such as anionic polymerization, except that the type of monomer used is also capable of radical polymerization. It is not particularly limited, and it may be a copolymer.

[0033] The plurality of polymer moieties have two or more different compositions. The difference in the composition is, when derived from a homopolymer, the difference between the monomer units constituting the polymer, and when derived from the copolymer, the difference between the monomer units and / or It is obtained by the difference of the unit ratio. The monomer unit is a monomer unit derived from the polymerizable unsaturated monomer described in the description of the hot melt resin composition of the fifth embodiment.

The combination of polymer portions having different compositions will depend on the performance (or use) required of the thermoplastic addition polymer. Basically, the combination of polymer portions includes a combination of polymer portions derived from polymers having different glass transition temperatures (Tg). As a combination of polymers having different Tg, for example, a combination of a polymer portion having a Tg of 0 ° C. or less and a polymer portion having a Tg of 20 ° C. or more, preferably a polymer having a Tg of −20 ° C. or less Combination with a polymer part having a Tg of 50 ° C. or more, more preferably −40 ° C.
Combinations of a polymer portion having the following Tg and a polymer portion having a Tg of 70 ° C. or higher can be given. By selecting these combinations, it is possible to achieve conflicting performances such as heat resistance and tackiness, and adhesive strength and toughness. For example, a hot melt resin composition is used as a pressure-sensitive adhesive (pressure-sensitive adhesive).
When used as a polymer, the polymer portion having a low Tg
The thermoplastic addition polymer is designed to occupy more, more than more, of the high polymer fraction.

When the hot-melt resin composition is used as a hot-melt adhesive, the thermoplastic addition polymer is used so that the polymer portion having a high Tg occupies a larger portion or a larger portion than the polymer portion having a lower Tg. Is designed. The thermoplastic addition polymer of the hot melt resin composition according to the first aspect is produced, for example, by the method for producing a thermoplastic addition polymer of the hot melt resin composition according to the fifth or sixth aspect. [Hot-melt resin composition according to the second embodiment] The hot-melt resin composition of the present invention, according to the second embodiment, comprises a thermoplastic addition polymer having a polyvalent mercaptan portion and a plurality of polymer portions. Including. The thermoplastic addition polymer is
It has a number average molecular weight of 10,000 to 200,000.
The plurality of polymer moieties have two or more different compositions and extend radially from the polyvalent mercaptan moiety to each other.
Has a composition that changes with a gradient composition, that is, a composition that changes continuously throughout the aggregate of the thermoplastic addition polymer.

The hot melt resin composition according to the second aspect is the hot melt resin composition according to the first aspect, in which a plurality of polymer portions have a gradient composition in which each other has a gradient composition.
This is the same as the hot-melt resin composition according to the first embodiment except that the composition has a composition that changes . The polymer portion is composed of two or more different polymerizable unsaturated monomer units. The polymerizable unsaturated monomer unit is a monomer unit derived from a polymerizable unsaturated monomer mentioned in the description of the hot melt resin composition of the fifth embodiment described later. The two or more different polymerizable unsaturated monomer units are
A unit derived from a first polymerizable unsaturated monomer (first monomer unit) capable of forming a polymer portion of the first polymer portion, and a second polymer having different physical properties from the first polymer portion And a unit derived from a second polymerizable unsaturated monomer capable of forming a portion (a second monomer unit).

The polymer parts have a gradient in their composition.
It has a composition that changes with the composition. This is because the polymer portion does not consist of only the first polymer portion and the second polymer portion in the entire assembly, but the composition of the first polymer portion and the second polymer portion. That is, the composition of the coalesced portions has a continuous gradient composition mixed in any ratio. The composition of the polymerizable unsaturated monomer units is shown in an averaged form for the entire assembly.

The thermoplastic addition polymer of the second embodiment may be a polymer having only a polymer portion having the above-mentioned averaged monomer unit composition, or a polymer having the first polymer portion and the second polymer portion. The composition of the polymer portion has a continuous composition mixed at an arbitrary ratio, but exhibits different physical properties from a mixture of a copolymer having no block structure. In addition, the first polymer portion and the second polymer It shows different physical properties from a so-called block polymer or graft polymer having a united portion.

The thermoplastic addition polymer according to the second aspect can have various functions by having a polymer portion having a large number of compositions, when viewed as a whole assembling of the macromolecules constituting the polymer. In addition, since many compositions are slightly different from each other as a whole, a phase is hardly generated. Such a form effectively acts on the expression of a new function.

A large number of compositions means that the polymer portion has a composition composed of continuously changing constituent monomer units as a whole. For example, in a polymer having a wide glass transition point, the The upper limit of the glass transition temperature peak is determined from the composition of the monomer unit constituting the polymer portion having the lower limit of the glass transition temperature by a differential scanning calorimeter (DSC) so as to have a typical glass transition point. Has a composition up to the composition of the monomer units constituting the polymer portion having the glass transition point.

A large number of slightly different compositions means that the ratio of a part or all of the constituent monomer units of the polymer portion changes continuously, and that the ratio of the polymerizable unsaturated monomer in the polymerization system is changed. Obtained by gradually changing the composition. The reason for gradually changing the monomer composition in the polymerization system is, for example, that the second polymerization is carried out before or during the polymerization of the polymerization system containing the first polymerizable unsaturated monomer. It can be performed by gradually adding a polymerizable unsaturated monomer.

In the thermoplastic addition polymer of the second embodiment, 3
It is also possible to provide more various performances by combining the polymer portions having different compositions described above. The thermoplastic addition polymer of the hot melt resin composition according to the second embodiment is, for example, a method for producing a thermoplastic addition polymer of the hot melt resin composition according to the fifth or sixth embodiment, in particular, the first method. This is produced when a second polymerizable unsaturated monomer is gradually added to a mixture containing a polymerizable unsaturated monomer and a polyvalent mercaptan. The thermoplastic addition polymer of the hot melt resin composition according to the second embodiment prepared by this method contains sulfur atoms in the range of 0.005 to 4% by weight. If the amount of the sulfur atom is less than the above range, the number average molecular weight may be too large or a thermoplastic addition polymer having a desired structure may not be obtained. There is a possibility that physical properties derived from the composition of the above may not be easily exhibited. Since the number average molecular weight of the target thermoplastic addition polymer is 10,000 to 200,000, the amount of the sulfur atom is preferably in the range of 0.01 to 2% by weight, and the preferable number average molecular weight is 30,000. Since it is １５０150,000, the range of 0.02 to 1% by weight is more preferable. [Hot Melt Resin Composition According to Third Aspect] The hot melt resin composition of the present invention according to the third aspect contains a thermoplastic addition polymer. The thermoplastic addition polymer is 1
Having a number average molecular weight of 0000 to 200,000,
It has only one glass transition temperature peak having a width of 0 ° C. or more, and has a parallel light transmittance of 85% or more.

The thermoplastic addition polymer according to the third embodiment is obtained by defining the thermoplastic addition polymer according to the second embodiment by physical properties. In the third aspect, the thermoplastic addition polymer preferably has a glass transition temperature peak having a width of 80 ° C. or more. In a third aspect, the thermoplastic addition polymer is preferably between 30,000 and 150,000.
And has only one glass transition temperature peak having a width of 80 ° C. or more and a parallel light transmittance of 90% or more. One example of such a thermoplastic addition polymer is the thermoplastic addition polymer according to the second embodiment.

The thermoplastic addition polymer according to the third embodiment contains, for example, two or more different polymerizable unsaturated monomer units. Examples of the two or more different polymerizable unsaturated monomer units include the first monomer unit and the second monomer unit described in the description of the second embodiment. When the number average molecular weight of the thermoplastic addition polymer is below the above range, physical properties derived from the composition of the monomer units constituting the polymer are difficult to develop, and when the number average molecular weight exceeds the range, the viscosity is high and the handling is difficult.

The thermoplastic addition polymer has only one glass transition temperature peak having a width of 50 ° C. or more, preferably 80 ° C. or more. If the width of the glass transition temperature peak falls below the above range, the balance between the heat resistance and the toughness of the polymer will be poor. The width of the glass transition temperature peak is 8 more than 50 ° C or more.
A temperature of 0 ° C. or higher is preferred in terms of a balance between heat resistance and toughness. In addition, the width of the glass transition temperature peak indicates a peak width measured by a differential scanning calorimeter (DSC).

The thermoplastic addition polymer has a parallel light transmittance of 85% or more. When the parallel light transmittance is lower than the above range, it indicates that the phase separation state of the polymer is large. A parallel light transmittance of 90% or more is more preferable than 85% for use in applications requiring transparency. The parallel light transmittance is a visible light transmittance measured by a turbidimeter in the thickness direction of a 3 mm-thick flat plate obtained by injection-molding a thermoplastic addition polymer.

The thermoplastic addition polymer of the hot melt resin composition according to the third embodiment may be, for example, a fifth or sixth thermoplastic polymer.
The method for producing a thermoplastic addition polymer of a hot melt resin composition according to the aspect of the present invention, in particular, the second polymerizable while polymerizing to a mixture containing a first polymerizable unsaturated monomer and a polyvalent mercaptan Created when the unsaturated monomer is added slowly. The thermoplastic addition polymer of the hot melt resin composition according to the third embodiment produced by this method contains sulfur atoms in the range of 0.005 to 4% by weight. If the amount of the sulfur atom is less than the above range, the number average molecular weight may be too large or a thermoplastic addition polymer having a desired structure may not be obtained. There is a possibility that physical properties derived from the composition of the above may not be easily exhibited. The number of sulfur atoms is such that the number average molecular weight of the target thermoplastic addition polymer is 10,000 to 20%.
Since it is 0000, the range of 0.01 to 2% by weight is preferable, and the preferable number average molecular weight is 30,000 to 1%.
Since it is 50,000, the range of 0.02 to 1% by weight is more preferable. [Hot Melt Resin Composition According to Fourth Aspect] According to the fourth aspect of the hot melt resin composition of the present invention, the first
In the hot melt resin composition according to any one of the embodiments to the third embodiment, the thermoplastic addition polymer comprises a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. Have been.

In the hot melt resin composition according to the fourth aspect, the thermoplastic addition polymer is composed of a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. Except for the above, it is the same as the hot melt resin composition according to any of the first to third aspects. The carboxyl group-containing polymerizable unsaturated monomer unit is, for example, a monomer unit derived from a carboxyl group-containing polymerizable unsaturated monomer described in a fifth embodiment described later.

The (meth) acrylate monomer unit is, for example, a monomer unit derived from the (meth) acrylate monomer described in the fifth embodiment described later. In the hot melt resin composition according to the fourth aspect, the thermoplastic addition polymer is, for example, 0.5 to 25% by weight of a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer. Other polymerizable unsaturated monomer units 0 to 25 copolymerizable with 75 to 99.5% by weight of units.
%, Preferably 1 to 10% by weight of a carboxyl group-containing polymerizable unsaturated monomer unit and 90 to 99% by weight of a (meth) acrylate monomer unit.

The amount of the carboxyl group-containing polymerizable unsaturated monomer unit is set within the above range in order to introduce a carboxyl group into the thermoplastic addition polymer.
The heat resistance of the hot melt resin composition may be insufficient, and if it exceeds, the performance such as water resistance of the hot melt resin composition may be adversely affected. When the amount of the (meth) acrylate monomer unit is within the above range, the heat resistance and weather resistance of the hot melt resin composition are good.

The other polymerizable unsaturated monomer unit which can be copolymerized is, for example, a monomer unit derived from a copolymerizable polymerizable unsaturated monomer described in the fifth embodiment described later. . If the amount of the polymerizable unsaturated monomer unit that can be copolymerized exceeds the above range, sufficient weather resistance may not be obtained.
The thermoplastic addition polymer of the hot melt resin composition according to the fourth aspect may be, for example, a method for producing a thermoplastic addition polymer of a hot melt resin composition according to the fifth or sixth aspect, which comprises a carboxyl group-containing polymer. It is produced when a polymerizable unsaturated monomer containing a polymerizable unsaturated monomer and a (meth) acrylate monomer is used. [Hot Melt Resin Composition According to Fifth Aspect] According to the fifth aspect, the hot melt resin composition of the present invention is a thermoplastic resin obtained by a production method including a preparation step, an addition step, and a polymerization step. Including addition polymers.

The preparation step is a step of preparing a mixture containing the first polymerizable unsaturated monomer and a polyvalent mercaptan. As the first polymerizable unsaturated monomer, any monomer can be used as long as it forms a homopolymer or a copolymer by radical polymerization. For example,
(Meth) acrylic acid; an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate,
(Meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate; styrene-based polymerizable polymers such as α-methylstyrene, vinyltoluene, and styrene Monomers; vinyl ethers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl acetate, etc .; fumaric acid, monoalkyl esters of fumaric acid, dialkyl esters of fumaric acid; maleic acid, monoalkyl esters of maleic acid, maleic acid Acid dialkyl esters; itaconic acid, itaconic acid monoalkyl esters,
Dialkyl esters of itaconic acid; half esters of succinic or phthalic anhydride with hydroxyethyl (meth) acrylate; (meth) acrylonitrile, butadiene, isoprene, vinyl chloride, vinylidene chloride,
Examples thereof include vinyl ketone, vinyl pyridine, and vinyl carbazole.
These can be used together.

The polyvalent mercaptan is a compound having two or more mercapto groups per molecule. Mercaptans in which the number of mercapto groups per molecule is 2, 3,... Valuable mercaptans ... As polyvalent mercaptan, for example,
Diesters of diols such as ethylene glycol and 1,4-butanediol and carboxyl-containing mercaptans; compounds having three or more hydroxyl groups such as trimethylolpropane, pentaerythritol, dipentaerythritol and polyester compounds of carboxyl-containing mercaptans; Compounds having three or more mercapto groups such as trithioglycerin; 2-di-n-butylamino-
4,6-dimercapto-S-triazine, 2,4,6-
Triazine polyvalent thiols such as trimercapto-S-triazine; compounds obtained by adding hydrogen sulfide to a plurality of epoxy groups of a polyepoxy compound to introduce a plurality of mercapto groups; a plurality of carboxyl groups of a polyvalent carboxylic acid And an ester compound obtained by esterifying the compound with mercaptoethanol, and any of them can be used alone or in combination of two or more.
Here, the carboxyl group-containing mercaptans are compounds having one mercapto group and one carboxyl group, such as thioglycolic acid, mercaptopropionic acid, and thiosalicylic acid.

When the polymerization is carried out in the presence of a polyvalent mercaptan, the polymerization proceeds from the mercapto group of the polyvalent mercaptan as a starting point, so that the thermoplastic addition polymer has a narrow molecular weight distribution and a highly branched star-shaped block structure. Is generated. From the viewpoint of forming a polymer having a star block structure, the polyvalent mercaptan is preferably a compound having 3 to 6 mercapto groups (i.e., a 3 to 6 functional mercaptan), more preferably 4 to 6 compounds. Compound having a mercapto group (that is, 4 to 6 functional mercaptan)
It is. Mercaptans having only one mercapto group do not provide a radially extended structure of the polymer portion. A mercaptan having more than six mercapto groups does not have a structure extending radially from the same center, and thus may not exhibit desired physical properties.

Examples of the polyvalent mercaptan include trifunctional mercaptans such as trithioglycerin, trimethylolpropane trithioglycolate, and trimethylolpropane trithiopropionate; pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthioprolate. 4-functional mercaptans such as pionates; hexafunctional mercaptans such as dipentaerythritol hexakisthioglycolate and dipentaerythritol hexakisthiopropionate; compounds obtained by adding hydrogen sulfide to polyepoxy compounds, polycarboxylic acids And at least one of them.

The mixture prepared in the preparation step contains, for example, 0.01 to 10 parts by weight of a polyvalent mercaptan based on 100 parts by weight of the first polymerizable unsaturated monomer. When the amount of the polyvalent mercaptan is out of the above range, the number average molecular weight of the polymer portion is out of the range of 1,000 to 150,000, or the number average molecular weight of the thermoplastic addition polymer is 10,000.
Or out of the range of 200,000.
Considering this point, the amount of polyvalent mercaptan is 0.0
5 to 5 parts by weight are more preferred.

The mixture prepared in the preparation step dissolves and / or dissolves the first polymerizable unsaturated monomer and the polyvalent mercaptan.
Or it may further include a dispersed medium. The medium may be any medium in which the monomer and the obtained polymer are soluble. The amount of the medium is, for example, 0 to 200% by weight, preferably 0 to 100% by weight, based on the total amount of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer. . Exceeding the above range is not industrially preferable because the polymerization rate decreases and the cost in terms of solid content increases. Examples of the medium include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as hexane and pentane; Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone are exemplified. The organic solvent may be a single solvent or a mixed solvent.

In the adding step, a second polymerizable unsaturated monomer having a composition different from that of the first polymerizable unsaturated monomer is added to a mixture containing the first polymerizable unsaturated monomer and the polyvalent mercaptan. This is a step of adding a monomer. As the second polymerizable unsaturated monomer, one that produces a homopolymer or a copolymer by radical polymerization and has a composition different from that of the first polymerizable unsaturated monomer Any of these monomers can be used. For example, those exemplified as the first polymerizable unsaturated monomer can be exemplified, and any of them can be used alone or in combination of two or more.

When the hot-melt resin composition is used as a pressure-sensitive adhesive (pressure-sensitive adhesive), it is necessary that the polymer portion having a low Tg occupy more or more of the polymer portion having a high Tg. A plastic addition polymer is designed. When using the hot melt resin composition as a hot melt adhesive, the design of the thermoplastic addition polymer is designed so that the polymer portion having a high Tg occupies a larger portion than the polymer portion having a lower Tg. Done.

The combination of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer is obtained by introducing a block structure having a polymer portion having a different Tg to form a thermoplastic addition polymer. For example, a polymerizable unsaturated monomer capable of forming a thermoplastic polymer having a glass transition point of 0 ° C. or lower and a thermoplastic polymer having a glass transition point of 20 ° C. or higher are set from the viewpoint of increasing cohesive force. A combination with a polymerizable unsaturated monomer capable of forming a coalescence is exemplified. From the viewpoint of further improving the cohesive strength of the thermoplastic addition polymer, preferably, a polymerizable unsaturated monomer capable of producing a thermoplastic polymer having a glass transition point of -20 ° C or less, and 50 ° C or more In combination with a polymerizable unsaturated monomer capable of producing a thermoplastic polymer having a glass transition point of, more preferably-
A polymerizable unsaturated monomer capable of forming a thermoplastic polymer having a glass transition point of 40 ° C. or lower, and a polymerizable unsaturated monomer capable of forming a thermoplastic polymer having a glass transition point of 70 ° C. or higher It is a combination with

At this time, the first polymerizable unsaturated monomer and the second
Of the polymerizable unsaturated monomers, one is a monomer capable of producing a thermoplastic polymer having a low glass transition point, and the other is a monomer capable of producing a thermoplastic polymer having a high glass transition point. There is no particular limitation if it exists. 0.5 to 25% by weight of a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer as the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer When 75 to 99.5% by weight is used, the heat resistance is improved by the carboxyl group introduced into the thermoplastic addition polymer, and the thermoplastic addition polymer becomes (meth)
The improvement in weather resistance due to the acrylic resin is recognized, which is more preferable.

The carboxyl group-containing polymerizable unsaturated monomers include, for example, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, and itaconic acid. It is at least one monomer selected from the group consisting of monoalkyl esters of unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and half esters of succinic anhydride or phthalic anhydride and hydroxyethyl (meth) acrylate. . If the amount of the carboxyl group-containing polymerizable unsaturated monomer is less than the above range, the heat resistance of the hot melt resin composition may be insufficient, and if the amount exceeds the above range, the hot melt resin composition may have an adverse effect on performance such as water resistance. May cause.

The (meth) acrylic acid ester monomer is, for example, an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, hydroxyethyl (meth)
From the group consisting of (meth) acrylates represented by acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate At least one monomer selected. When the amount of the (meth) acrylate monomer is within the above range, the heat resistance and the weather resistance of the hot melt resin composition are good.

The polymerizable unsaturated monomer copolymerizable is a monomer copolymerizable with a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer. And the monomers other than the carboxyl group-containing polymerizable unsaturated monomer and the (meth) acrylate monomer among the polymerizable unsaturated monomers exemplified in (1). If the amount of the copolymerizable polymerizable unsaturated monomer exceeds the above range, sufficient weather resistance may not be obtained.

The amount of the second polymerizable unsaturated monomer is, for example, in the range of 5 to 2,000 parts by weight based on 100 parts by weight of the polymer formed from the first polymerizable unsaturated monomer. Outside of this range, the thermoplastic addition polymer may not have the performance derived from the star block structure. Considering this point, the amount of the second polymerizable unsaturated monomer is 10 to 10
00 parts by weight is preferred.

In the addition step, a method of adding the second polymerizable unsaturated monomer in a lump or a method of gradually adding the second polymerizable unsaturated monomer can be adopted. The polymerization step is a step of performing radical polymerization of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer starting from the mercapto group of the polyvalent mercaptan. The polymerization step can be performed during the addition step or after the addition step. When the polymerization step is performed during the addition step, radical polymerization is performed while gradually adding the second polymerizable unsaturated monomer. When the polymerization step is performed after the addition step, between the preparation step and the addition step, a prepolymerization step of performing radical polymerization of the first polymerizable unsaturated monomer starting from the mercapto group of the polyvalent mercaptan is further performed. Can be included.

The radical polymerization can be carried out by a conventional radical polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. In order to obtain an inexpensive polymer, a bulk polymerization method containing no extra volatile components is preferable. The polymerization temperature is preferably from 30 to 200 ° C., more preferably from 100 to 1 to allow stable bulk polymerization without using a polymerization initiator.
50 ° C.

In the polymerization step, a conventional radical polymerization initiator (for example, 2,2'-azobisisobutyronitrile,
Azo-based polymerization initiators such as 2,2'-azobiscyclohexanecarbonitrile; peroxide-based polymerization initiators such as benzoyl peroxide) can be used.
It is not more than 1/3, preferably not more than 1/10, more preferably not used, of the polyvalent mercaptan. When the polymerization initiator is used in a larger amount than the above ratio, in addition to the polymer portion extended from the polyvalent mercaptan, a large amount of the polymer extended from the polymerization initiator is generated, and the thermoplastic addition polymer having a star block structure Generation efficiency is reduced.

By the radical polymerization, a product is obtained in which, in each molecule of the polyvalent mercaptan, one or a plurality of sulfur residues of a mercapto group are bonded to a carbon atom at one end of a carbon chain of a polymer portion. This product has unreacted mercapto groups. In order to efficiently bind one end of the polymer portion to the sulfur residue, it is preferable not to add an unnecessary polymerization initiator to the polymerization system. The plurality of polymer parts formed by performing radical polymerization of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer have two or more different compositions.

In the fifth embodiment, in the case where the second polymerizable unsaturated monomer is gradually added in the addition step and the polymerization step is performed in the addition step, the polymer portion is continuously formed as a whole. Is obtained, and a thermoplastic addition polymer having a polymer portion having a so-called gradient composition (or a thermoplastic addition polymer of the hot melt resin composition according to the second or third embodiment) is obtained. In this case, as described above, the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer are used as the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer. When the carboxyl group-containing polymerizable unsaturated monomer 0.5 to 25% by weight and the (meth) acrylate monomer 75 to 99.5% by weight are used as the saturated monomers, the fourth embodiment Thus, a thermoplastic addition polymer of the hot melt resin composition is obtained.

The reaction mixture obtained in the polymerization step can be used as it is as a hot melt resin composition when it does not contain volatile components such as a solvent and residual monomers. When the reaction mixture contains a volatile component, a hot melt resin composition is obtained by removing the volatile component using a device such as a twin screw extruder or a thin film evaporator. [Hot Melt Resin Composition According to Sixth Aspect] The hot melt resin composition of the present invention, according to the sixth aspect, is obtained by a production method including a preparation step, a prepolymerization step, an addition step, and a polymerization step. Containing thermoplastic addition polymers.

The preparation step is a step of preparing a mixture containing the first polymerizable unsaturated monomer and the polyvalent mercaptan, and is as described in the fifth embodiment. The prepolymerization step is a first polymerization step in which radical polymerization of the first polymerizable unsaturated monomer is performed starting from the mercapto group of the polyvalent mercaptan. The conditions (temperature, time, raw material ratio, etc.) and method of polymerization may be the same as those described in the fifth embodiment.

In the prepolymerization step, radical polymerization of the first polymerizable monomer component is carried out in the presence of a polyvalent mercaptan. To the addition step. When the addition step is performed after the polymerization rate becomes 50% or more, preferably 80% or more, it is assumed that the polymerization step is performed without removing the remaining first polymerizable unsaturated monomer. Also, different polymer portions are likely to be generated in the pre-polymerization step and the polymerization step. It is also possible to volatilize off the remaining first polymerizable unsaturated monomer after the pre-polymerization step to produce different polymer moieties.

In the addition step, a second polymerizable unsaturated monomer having a composition different from that of the first polymerizable unsaturated monomer is added to the reaction mixture obtained in the prepolymerization step, and the second mixture is obtained. This is the step of obtaining At this time, a method of adding the second polymerizable unsaturated monomer at a time, a method of gradually adding the second polymerizable unsaturated monomer, and the like can be adopted. The polymerization rate of the pre-polymerization step is 50% or more,
If the second polymerizable unsaturated monomer is added all at once after volatilizing and removing the remaining polymerizable unsaturated monomer as necessary,
A thermoplastic addition polymer having polymer portions of different compositions is obtained. 0-50% polymerization rate in pre-polymerization step
When the second polymerizable unsaturated monomer is gradually added after the above, a thermoplastic addition polymer having a polymer portion having a so-called gradient composition in which the polymer portion continuously changes in composition as a whole. Is obtained.

The polymerization step is a second polymerization step in which the polymerizable unsaturated monomer contained in the second mixture is subjected to radical polymerization starting from the mercapto group of the polyvalent mercaptan. The conditions (temperature, time, raw material ratio, etc.) and method of polymerization may be the same as those described in the fifth embodiment. In the polymerization step, in the presence of the product of the previously performed radical polymerization, a polymerizable unsaturated monomer having a composition different from that of the polymerizable unsaturated monomer used in the previously performed radical polymerization Perform radical polymerization. If necessary, unreacted monomer components may be removed from the reaction mixture containing the product of the previous radical polymerization, or the unreacted monomer components may be left without being removed. Alternatively, it can be used for the subsequent radical polymerization. The subsequent radical polymerization
The reaction is performed starting from all or a part of the remaining mercapto groups in the polyvalent mercaptan. A product is obtained in which one end of a polymer portion having another composition is bonded to the sulfur residue of the mercapto group serving as the starting point. This product may have unreacted mercapto groups. In this case, by repeating the second polymerization step twice,
By introducing a polymer portion having a different composition from the above and repeating the second polymerization step three times, a polymer portion having a third and fourth different composition is introduced and the number of repetitions of the second polymerization step is increased. Further, it is possible to introduce a polymer portion having a different composition.

After completion of the addition of the second polymerizable unsaturated monomer,
If necessary, radical polymerization for aging can be performed. When the reaction mixture obtained in the polymerization step does not contain a volatile component such as a solvent or a residual monomer, it can be used as a hot melt resin composition as it is. When the reaction mixture contains a volatile component, a hot melt resin composition is obtained by removing the volatile component using a device such as a twin screw extruder or a thin film evaporator.

In the sixth embodiment, the polymerization rate in the prepolymerization step is set to 50% or more, and the second polymerizable unsaturated monomer is added at once after volatilization and removal of the remaining polymerizable unsaturated monomer as required. In this case, a thermoplastic addition polymer having a polymer portion having two different compositions (or a thermoplastic addition polymer of the hot melt resin composition according to the first embodiment) is obtained. In this case, as described in the fifth embodiment, the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer are used as the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer.
When 0.5 to 25% by weight of a carboxyl group-containing polymerizable unsaturated monomer and 75 to 99.5% by weight of a (meth) acrylate monomer are used as the polymerizable unsaturated monomers, A thermoplastic addition polymer of the hot melt resin composition according to the fourth aspect is obtained.

In the sixth embodiment, the polymerization rate in the pre-polymerization step is set to 0 to 50%, and the second polymerizable unsaturated monomer is gradually removed after volatilization and removal of the remaining polymerizable unsaturated monomer as necessary. When added, the monomer composition in the polymerization system gradually changes. As a result, the composition of the obtained copolymer portion gradually changes, and a thermoplastic addition polymer having a number of slightly different compositions (gradient compositions) can be obtained.
Moreover, since radical polymerization is performed starting from the mercapto group of the polyvalent mercaptan, a thermoplastic addition polymer in which a polymer portion having an arbitrary composition is bonded from the polyvalent mercaptan portion by the valency of the mercapto group, that is, the polymer portion, A thermoplastic addition polymer having a polymer portion consisting of a so-called gradient composition in which the composition continuously changes as a whole (or,
The thermoplastic addition polymer of the hot melt resin composition according to the second aspect) is obtained. In this case, even if the polymer capable of forming the first polymerizable unsaturated monomer and the polymer capable of forming the second polymerizable unsaturated monomer are incompatible,
For example, a thermoplastic addition polymer having a parallel light transmittance of 85% or more, preferably 90% or more (or a thermoplastic addition polymer of the hot melt resin composition according to the third embodiment) can be obtained. Here, that the polymers are not compatible means that the mixture of the polymers has undergone phase separation, and has a form such as a sea-island structure. First
As the polymerizable unsaturated monomer and the second polymerizable unsaturated monomer, as described in the fifth embodiment, the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer As a monomer, a carboxyl group-containing polymerizable unsaturated monomer 0.5 to 2
5% by weight and (meth) acrylate monomer 75 to 9
When 9.5% by weight is used, a thermoplastic addition polymer of the hot melt resin composition according to the fourth embodiment is obtained. [Hot Melt Resin Composition According to Seventh Aspect] According to the seventh aspect, the hot melt resin composition of the present invention has a star-shaped structure obtained by a production method including a preparation step and a polymerization step. Including a plastic addition polymer. The preparation step is a step of preparing a mixture containing a polymerizable unsaturated monomer comprising a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer and a polyvalent mercaptan. The polymerization step is a step of performing radical polymerization of a polymerizable unsaturated monomer starting from a mercapto group of a polyvalent mercaptan.

The hot melt resin composition according to the seventh aspect is characterized in that the polymerizable unsaturated monomer comprises a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer, Is performed as described in the fifth embodiment, except that the polymerization is not performed and the radical polymerization of the polymerizable unsaturated monomer contained in the mixture obtained in the preparation step is performed in the polymerization step.

In the polymerization step, the mixture obtained in the preparation step is charged at once or gradually added to the polymerization system to perform radical polymerization. The polymerization is preferably bulk polymerization or solution polymerization. The polymerization temperature is, for example, 20 to 180 ° C, preferably 100 to 150 ° C. Most preferably, no polymerization initiator is used, and even if used, it is used in an amount of 1/3 or less, preferably 1/10 or less, based on the weight of the polyvalent mercaptan. If the amount of the polymerization initiator exceeds the above range, a large amount of linear polymer may be formed as a by-product, and a thermoplastic addition polymer having a star structure may not be obtained.

Carboxyl group-containing polymerizable unsaturated monomer
The (meth) acrylate monomer is as described in the fifth embodiment. [Hot-melt resin composition according to the eighth aspect] According to the eighth aspect, the hot-melt resin composition according to the present invention provides the hot-melt resin composition according to any one of the first to seventh aspects. The article further includes a metal ion source.

The metal ion source is contained in the hot melt resin composition by mixing with a reaction mixture containing a thermoplastic addition polymer obtained by polymerization, for example. Mixing can be performed by a direct heating mixing device such as a twin screw extruder, a kneader, and a heating roller. Before or after removing volatile components from the reaction mixture, a metal ion source may be mixed to obtain a hot melt resin composition.

Examples of the metal ion source include oxides, hydroxides, alcoholates, and organic carboxylate salts of metals such as sodium, potassium, lithium, magnesium, calcium, and zinc. One compound is used. In order to suppress the viscosity at the time of the hot melt operation, it is preferable to add 0.1 to 0.9 equivalent of metal ion to the carboxyl group of the thermoplastic addition polymer, more preferably 0.2 to 0.9.
~ 0.6 equivalents. If the metal ion is less than the above range, the heat resistance during use will be insufficient, and if it is more than the above range, it will be difficult to balance the performance of the hot melt resin composition, for example, the viscosity during hot melt operation will increase. [Hot melt resin composition according to ninth aspect] According to the ninth aspect, the hot melt resin composition of the present invention further includes a phosphate in the hot melt resin composition according to the eighth aspect. .

When the hot melt resin composition contains a phosphate, the hot melt workability of the hot melt resin composition is improved. Phosphate esters are, for example,
It is contained in the hot melt resin composition by being mixed with a reaction mixture containing a thermoplastic addition polymer obtained by polymerization. Before or after removing volatile components from the reaction mixture, a phosphate ester may be mixed to obtain a hot melt resin composition.

The phosphoric acid ester is, for example, at least one compound selected from the group consisting of monoesters, diesters and triesters of an alkyl group having 1 to 18 carbon atoms. 4 ~
It is at least one compound selected from the group consisting of monoester, diester and triester of eight alkyl groups. The amount of the phosphate ester is, for example, 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the thermoplastic addition polymer. If the ratio is below the above range, the hot melt workability may not be improved, and if it is above the range, the heat resistance may be insufficient. [Hot Melt Resin Composition According to Tenth Aspect] According to the tenth aspect, the hot melt resin composition of the present invention comprises a (meth) acrylic thermoplastic addition polymer, a metal ion source, and a phosphate ester. including. The (meth) acrylic thermoplastic addition polymer contains a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit as essential components, and can be copolymerized as necessary. Contains a polymerizable unsaturated monomer unit.

The number average molecular weight of the (meth) acrylic thermoplastic addition polymer is the same as that of the thermoplastic addition polymer described in the first embodiment. The carboxyl group-containing polymerizable unsaturated monomer unit / (meth) acrylate monomer unit is as described in the fourth embodiment. The polymerizable unsaturated monomer unit which can be copolymerized is, among the polymerizable unsaturated monomers described in the fifth embodiment, a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylic ester monomer. It is a unit derived from a monomer other than the carboxyl group-containing polymerizable unsaturated monomer and the (meth) acrylate monomer, which is copolymerizable with the polymer.

The (meth) acrylic thermoplastic addition polymer can be obtained, for example, by adding the first polymerizable unsaturated monomer or the second polymerizable unsaturated monomer described in the fifth embodiment to a polyvalent mercaptan. It is produced by a method of radical polymerization in the presence of a polymerization initiator without using a polymer. The type of polymerization initiator is
For example, as described in the fifth mode.
The amount of the polymerization initiator is not particularly limited. The polymerization temperature is, for example, as described in the fifth embodiment. Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.

The metal ion source is as described in the eighth embodiment. The phosphate ester is as described in the ninth embodiment. [Hot melt resin composition according to eleventh aspect] The hot melt resin composition according to the eleventh aspect, according to the eleventh aspect, is a hot melt resin composition according to any one of the first to tenth aspects. The article further includes a tackifier.

Examples of the tackifier include rosin resin, terpene resin, aliphatic petroleum resin, aromatic petroleum resin, cumarone-indene resin, alkylphenol resin, xylene resin and the like. Use one or more of these resins. The tackifier has a function of reducing the viscosity at the time of hot melt operation and improving the cohesive force at the time of use. The amount of the tackifier used is, for example, 1 to 100 parts by weight of the hot melt resin composition according to any of the first to tenth aspects.
It is from 200 to 200 parts by weight, preferably from 10 to 100 parts by weight. If it is less than the above range, the viscosity may not be reduced or the cohesive strength may not be improved, and if it exceeds, the tack may be reduced or the cohesive force may be insufficient when the hot melt resin composition is used as an adhesive. May be.

The tackifier is contained in the hot melt resin composition, for example, by mixing with a reaction mixture containing a thermoplastic addition polymer obtained by polymerization. Before or after removing volatile components from the reaction mixture, a tackifier may be mixed to obtain a hot melt resin composition. [Hot melt resin composition according to twelfth aspect] According to the twelfth aspect, the hot melt resin composition according to the twelfth aspect is the hot melt resin composition according to any one of the first aspect to the eleventh aspect. The article further includes a wax.

Examples of the wax include natural wax, paraffin wax, polypropylene wax, polyethylene wax, (meth) acrylate polymers having a saturated alkyl group having 18 or more carbon atoms, and the like. Use one or more waxes. Wax has a viscosity lowering effect during hot melt operation. The amount of the wax used is determined by the amount of the hot melt resin composition 1 according to any of the first to eleventh embodiments.
The amount is, for example, 1 to 100 parts by weight, preferably 10 to 50 parts by weight with respect to 00 parts by weight. If it is lower than the above range, the effect of lowering the viscosity may not be exhibited.

The wax is included in the hot melt resin composition, for example, by mixing with a reaction mixture containing a thermoplastic addition polymer obtained by polymerization. Before or after removing volatile components from the reaction mixture, wax may be mixed to obtain a hot melt resin composition. [Each hot melt resin composition from first aspect to twelfth aspect] Each hot melt resin composition from first aspect to twelfth aspect further includes other additives as necessary. You may go out. As the additive, for example, a compound serving as a plasticizer of a (meth) acrylate polymer such as a phthalate ester and an adipic ester;
It is at least one compound selected from the group consisting of fillers such as silica powder and titanium oxide; and antioxidants such as dithiocarbamates and phenol compounds. Examples of the amounts of these additives include the amounts used in conventional hot melt resin compositions.

The additives are contained in the hot melt resin composition by, for example, mixing with a reaction mixture containing a thermoplastic addition polymer obtained by polymerization. Before or after removing volatile components from the reaction mixture, additives may be mixed to obtain a hot melt resin composition.

[0094]

EXAMPLES Examples of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. In the following, “%” means “% by weight” and “parts” means “parts by weight”. In addition, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) in terms of polystyrene.

The glass transition temperature (Tg) was measured using a differential scanning calorimeter “DSC- manufactured by Perkin Elmer”.
7 ". The parallel light transmittance was measured using a turbidimeter (ND-1001DP, Nippon Denshoku Industries Co., Ltd.) in the thickness direction of a 3 mm-thick flat plate obtained by injection-molding a polymer. (Example 1) Max blend blade equipped with a nitrogen inlet tube, a dropping funnel, a thermometer, and a cooling tube (Sumitomo Heavy Industries, Ltd.)
Methacrylate, 4 parts of acrylic acid, 0.2 parts of azobiscyclohexanecarbonitrile, 200 parts of methyl isobutyl ketone, 200 parts of pentaerythritol tetrakisthioglycolate. 6 parts were added, and polymerization was carried out at 100 ° C. under a nitrogen atmosphere. After 2 hours, the conversion of methyl methacrylate reaches 90%, the number average molecular weight Mn of the produced polymer is 1.4 × 10 ⁴ , the molecular weight distribution (Mw / Mn) is 1.8, and the glass transition temperature Tg is 89. ° C. Subsequently, 300 parts of butyl acrylate, 175 parts of 2-ethylhexyl acrylate, and 25 parts of acrylic acid were added all at once to the reaction solution from a dropping funnel. After a while, when the internal temperature increased, it was found that the reaction system became cloudy and the second-stage polymerization was started. After reacting at the reflux temperature for 5 hours, 0.14 parts of methoxyphenol as a polymerization inhibitor was added to terminate the polymerization. Volatile components such as methyl isobutyl ketone and residual monomers were volatilized and removed from the reaction solution thus obtained using a twin screw extruder to obtain a milky white polymer. The polymer has adhesive strength, Mn = 5.6 × 10 ⁴ , Mw
/Mn=2.4, Tg = −51 ° C. and 90 ° C. This polymer is referred to as hot melt resin composition (1).

In Example 1, the polymerization proceeds from the mercapto group as a starting point, and thus the obtained polymer is poly (methyl methacrylate / acrylic acid) which is a polymer derived from the first polymerizable unsaturated monomer. And poly (butyl acrylate / 2-ethylhexyl acrylate) which is a polymer derived from a monomer mixture of the remainder of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer. / Acrylic acid / methyl methacrylate) was thought to have a block structure in which the above polymer portion extended up to the number of mercapto groups around polyvalent mercaptan at the maximum.

The properties of the hot melt resin composition (1) were measured by the following methods, and the results are shown in Table 1. 180 ° C viscosity: The hot melt resin composition was heated to 180 ° C and melted, and measured by a flow tester (manufactured by Shimadzu Corporation). In addition, about 100 poise or less, the result measured with the B-type rotational viscometer is shown.

180 ° peel strength: 25 to 3 coating thickness
The hot-melt resin composition is melt-coated on a commercially available copy paper (60 g in basis weight) so as to have a thickness of 0 μm, and is stuck to stainless steel (SUS) as an adherend with a width of 25 mm.
After pressing back and forth with a 2 kg roller once, it is 300 mm after 20 minutes.
The copy paper was peeled from the stainless steel at 180 ° at a pulling rate of / min, and the strength was measured.

Ball tack: J. The measured values obtained by the Dow method under the conditions of an inclination angle of 30 degrees and a run length of 10 cm are shown. Holding force: 25mm × on stainless steel (SUS) plate
A commercial copy paper (basis weight 60 g) melt-coated with the hot melt resin composition with an adhesive area of 25 mm was attached and
Press and reciprocate once with a kg roller at a predetermined temperature (40 ° C, 80
C.) for 20 minutes, and a time (unit: mm) was measured until a load of 1 kg was applied to the copy paper and dropped or after 1 hour.

(Example 2) Polymer 1 obtained in Example 1
1.3 parts of zinc acetate were added to 00 parts, and
Kneaded for hours. Obtained hot melt resin composition (2)
Is shown in Table 1. (Example 3) To 100 parts of the polymer obtained in Example 1, 30 parts of styrene-based petroleum resin (tackifier) FTR6100 (manufactured by Mitsui Petrochemical Co., Ltd.) was added and kneaded at 180 ° C for 1 hour. Table 1 shows the adhesive properties of the obtained hot melt resin composition (3).

(Example 4) Polymer 1 obtained in Example 1
To 00 parts, 2.0 parts of zinc acetate and 1.0 part of tributyl phosphate as a phosphoric ester were added and kneaded under reduced pressure at 180 ° C. for 1 hour. Table 1 shows the adhesive properties of the obtained hot melt resin composition (4). (Example 5) Styrene 2 was added to a nitrogen-purged autoclave.
00 parts and 3 parts of trimethylolpropane trithioglycolate were charged and heated to 140 ° C. After 2 hours, the polymerization rate reached 91%, and the resulting polymer had Mn = 1.5 × 1.
^{0 4, Mw / Mn = 8.6} , was Tg = 90 ° C.. Subsequently, 450 parts of butadiene, 25 parts of acrylic acid, and 25 parts of acrylonitrile were added to the reaction solution under pressure to proceed with polymerization. After reacting at 140 ° C. for 5 hours, 0.14 parts of methoxyphenol as a polymerization inhibitor was added to terminate the polymerization. Volatile components were removed from the obtained reaction solution using a twin screw extruder to obtain a milky white polymer. The polymer is
Shows slight tackiness, Mn = 4.2 × 10 ⁴ , Mw /
Mn = 6.8, Tg = −55 ° C., 90 ° C.

In Example 5, as in Example 1, the polymerization proceeded starting from a mercapto group.
The polymer obtained in the above is polystyrene, which is a polymer from the first polymerizable unsaturated monomer, and the rest of the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer. It was easily imagined that poly (butadiene, acrylic acid, acrylonitrile, styrene), which is a polymer from a monomer mixture with the body, had a block structure radially extending from the polyvalent mercaptan portion.

To 100 parts of this polymer, 50 parts of a tackifier (FTR6100 described above) was added and kneaded at 180 ° C. for 1 hour. Table 2 shows the adhesive properties of the obtained hot melt resin composition (5). (Example 6) 0.5 part of magnesium acetate was added to 100 parts of the hot melt resin composition (5) obtained in Example 5, and kneaded at 180 ° C for 2 hours. Table 2 shows the adhesive properties of the obtained hot melt resin composition (6).

Example 7 Magnesium acetate was added to 100 parts of the hot melt resin composition (5) obtained in Example 5.
0 parts and 1.0 part of 2-ethylhexyl acid phosphate were added and kneaded under reduced pressure at 180 ° C. for 2 hours. Table 2 shows the adhesive properties of the obtained hot melt resin composition (7).

Example 8 To the same apparatus as in Example 1, 196 parts of methyl methacrylate, 4 parts of acrylic acid, 200 parts of methyl isobutyl ketone, and 5.5 parts of dipentaerythritol hexakisthiopropionate were added. Heated to 100 ° C. under nitrogen atmosphere. Thirty minutes later, when the conversion reached 30%, a mixture of 300 parts of butyl acrylate, 175 parts of ethyl acrylate, and 25 parts of methacrylic acid was dropped from the dropping funnel over 3 hours. Thereafter, polymerization was continued for 1 hour, and then 0.14 parts of methoxyphenol as a polymerization inhibitor was added to terminate the polymerization. Volatile components were removed from the obtained reaction solution using a twin screw extruder to obtain a transparent polymer. The polymer shows tackiness and Mn = 6.
8 × 10 ⁴ , Mw / Mn = 2.4, Tg is −40 ° C. to 8
It showed a wide range of values up to 0 ° C. From the polymerization technique, the first
From poly (methyl methacrylate / acrylic acid) (methyl methacrylate / acrylic acid = 98/2, weight ratio) which is a polymer of the polymerizable unsaturated monomer of the second polymerizable unsaturated monomer. Poly (butyl acrylate)
(Ethyl acrylate / methacrylic acid) (butyl acrylate / ethyl acrylate / methacrylic acid = 60/35/5,
(Weight ratio), the polymerization proceeded with the polyvalent mercaptan as a starting point, and a polyvalent mercaptan central star block polymer having a continuous composition change was obtained.

The adhesive properties of the resulting polymer as a hot melt resin composition (8) are shown in Table 3. (Example 9) 2.0 parts of sodium methoxide was added to 100 parts of the polymer obtained in Example 8, and a hydrogenated rosin-based tackifier F was added.
20 parts of oral 105 (manufactured by Rika Hercules Co., Ltd.) was added and kneaded under reduced pressure at 180 ° C. for 1 hour. Table 3 shows the adhesive properties of the obtained hot melt resin composition (9).

Example 10 To 100 parts of the polymer obtained in Example 8, 3.0 parts of zinc acetate and 2.0 parts of 2-ethylhexyl acid phosphate were added, and the mixture was kneaded under reduced pressure at 180 ° C. for 1 hour. . Table 3 shows the adhesive properties of the hot melt resin composition (10). (Example 11) Vinyl acetate 2 was added to the same apparatus as in Example 1.
00 parts, butyl acrylate 150 parts, butyl acetate 300
And 4.0 parts of pentaerythritol tetrakisthioglycolate, and heated to 100 ° C. under a nitrogen atmosphere. When the polymerization rate was 10%, a mixture consisting of 335 parts of styrene and 15 parts of acrylonitrile was dropped from the dropping funnel over 3 hours. Thereafter, polymerization was continued for 1 hour, and then 0.14 parts of methoxyphenol as a polymerization inhibitor was added to terminate the polymerization. After adding and mixing 3 parts of an antioxidant (Sumilizer BP101 manufactured by Sumitomo Chemical Co., Ltd.) to the reaction solution thus obtained, volatile components were removed with a twin screw extruder. The resulting polymer was fluorescent color transparent, Mn = 5.1 × 10 ⁴ , Mw / Mn = 5.8, Tg = −.
It showed a wide value between 10 ° C and 90 ° C.

According to the polymerization technique, poly (vinyl acetate / butyl acrylate) (vinyl acetate / butyl acrylate = 57/43, weight ratio), which is a polymer derived from the first polymerizable unsaturated monomer, was converted to a second polymer. Poly (styrene / acrylonitrile) (styrene /
While gradually changing the composition to acrylonitrile (96/4, weight ratio), the polymerization proceeded with the polyvalent mercaptan as a starting point, thereby obtaining a polyvalent mercaptan central star block polymer having a continuous composition change.

The obtained polymer was used as a hot melt resin composition (11). Its viscosity at 180 ° C. and peel strength are shown in Table 4. The 180 ° C viscosity was measured by the method described above, and the peel strength was measured by the following method. Peel strength: SPCC steel plate (0.5 mm x 25 mm x 15
0 mm), the hot-melt resin composition was heated and melted so as to have a thickness of 20 to 30 μm, and the same steel sheet was quickly placed thereon, and pressed back and forth with a 2 kg roller once. After adjusting the temperature at a predetermined temperature (0 ° C., 25 ° C., 50 ° C.) for 20 minutes, the shear peel strength was measured at a tensile speed of 50 mm / min.

Example 12 In the same apparatus as in Example 1, 200 parts of vinyl acetate, 136 parts of butyl acrylate, 14 parts of 2-methacryloyloxyethyl acid phosphate (manufactured by Kyoeisha Resin Co., Ltd.), and 200 parts of butyl acetate And 5.6 parts of pentaerythritol tetrakisthioglycolate, and heated to 100 ° C. under a nitrogen atmosphere. 20% polymerization rate
335 parts of styrene and 15 parts of acrylonitrile
Parts of the mixture were dropped from the dropping funnel over 3 hours.

The thus obtained reaction solution was added to an antioxidant (S
After adding and mixing 3 parts of Umilizer BP101) and 7 parts of zinc acetate, volatile components were removed with a twin-screw extruder. The obtained hot melt resin composition (12) was transparent in fluorescent color, and the polymer before adding zinc acetate had Mn = 4.0 ×.
10 ⁴ , Mw / Mn = 4.8, and Tg = −8 ° C. to 89 ° C., showing a wide range of values.

The adhesive properties of the hot melt resin composition (12) are shown in Table 4. (Example 13) The resin composition (1) obtained in Example 12
2) 1.5 parts of 1-ethylhexyl acid phosphate was added to 100 parts and kneaded at 180 ° C. for 1 hour. Table 4 shows the adhesive properties of the obtained hot melt resin composition (13).
It was shown to.

Example 14 Mn = 10,000 Mw / M consisting of butyl acrylate / acrylic acid = 95/5
500 parts of a macromonomer having a methacryloyl group at one terminal with n = 1.9, 500 parts of ethyl acetate, and 5 parts of azobisisobutyronitrile were placed in the same flask as in Example 1, and heated to 70 ° C. under a nitrogen atmosphere. . When stirring was continued for 4 hours, the temperature was raised to 80 ° C., and the mixture was aged for 1 hour. Then, 0.14 part of methoxyphenol as a polymerization inhibitor was added to terminate the polymerization.

The volatile component was removed from the thus obtained reaction solution using a twin screw extruder to obtain a transparent polymer. The polymer has adhesive strength, Mn = 6.9 × 10 ⁴ , M
w / Mn = 3.5 and Tg = −50 ° C. Since the polymerization was performed only with the macromonomer, it was understood that the polymer had a highly branched structure.

Zinc acetate was added to 100 parts of this polymer.
0 parts and 2.0 parts of 2-ethylhexyl acid phosphate were added and kneaded under reduced pressure at 180 ° C. for 2 hours. Table 5 shows the adhesive properties of the hot melt resin composition (14) thus obtained. (Example 15) 425 parts of butyl acrylate, 50 parts of ethyl acrylate, and 25 parts of acrylic acid were added to the same apparatus as in Example 1.
30% of the mixture consisting of
Parts, 250 parts of toluene and 2.5 parts of azobisisobutyronitrile were added, and polymerization was carried out at 70 ° C. under a nitrogen atmosphere.

Twenty minutes after the start of the polymerization, the dropping of the monomer mixture was started and was completed in three hours. After completion of the dropwise addition, 1 part of azobisisobutyronitrile was charged, and polymerization was carried out for 1 hour. Then, 0.14 part of methoxyphenol was charged to terminate the polymerization. Volatile components were removed from the reaction solution thus obtained using a twin screw extruder to obtain a transparent polymer. The polymer has adhesive strength, Mn = 3.9 × 10 ⁴ , Mw / Mn = 7.
9, Tg = −45 ° C.

To 100 parts of this polymer was added 1 part of zinc acetate.
3 parts and 1.3 parts of 2-ethylhexyl acid phosphate were added and kneaded under reduced pressure at 180 ° C. for 2 hours. Table 5 shows the adhesive properties of the hot melt resin composition (16) thus obtained. (Comparative Example 1) To a device similar to that of Example 1, 50% of a mixed solution consisting of 425 parts of butyl acrylate, 50 parts of ethyl acrylate, and 25 parts of acrylic acid was added, and 500 parts of ethyl acetate was added.
Azobisisobutyronitrile (1.5 parts) was added and polymerization was carried out at 70 ° C. in a nitrogen atmosphere. Twenty minutes after the start of the polymerization, the dropping of the monomer mixture was started and completed in two hours. After completion of the dropwise addition, 1 part of azobisisobutyronitrile was charged, and polymerization was carried out for 1 hour. Then, 0.14 part of methoxyphenol was charged to terminate the polymerization.

The volatile component was removed from the thus obtained reaction solution using a twin screw extruder to obtain a transparent polymer. The polymer has an adhesive force, Mn = 7.8 × 10 ⁴ ,
Mw / Mn = 3.5 and Tg = −46 ° C. This polymer was used as a comparative hot melt resin composition (1), and its adhesive properties are shown in Table 5.

Comparative Example 2 A transparent polymer was obtained by repeating the operation of Comparative Example 1 except that the polymerization temperature was changed to 60 ° C. The polymer has an adhesive force, Mn = 9.5 × 10 ⁴ ,
Mw / Mn = 3.3 and Tg = −46 ° C. This polymer was used as a comparative hot melt resin composition (2), and its adhesive properties are shown in Table 5.

Comparative Example 3 A hot melt resin composition for comparison was prepared by adding 1.0 part of zinc acetate to 100 parts of the carboxyl group-containing polymer obtained in Example 15 and kneading under reduced pressure at 180 ° C. for 2 hours. (3) was obtained. Table 5 shows the adhesive properties.
Shown in (Comparative Example 4) To 100 parts of the polymer having a branched structure (without zinc acetate) obtained in Example 14, 30 parts of a tackifier (FTR6100 described above) was added and kneaded at 180 ° C for 1 hour. Table 5 shows the adhesive properties of the comparative hot melt resin composition (4) thus obtained.

(Comparative Example 5) In the same apparatus as in Example 1, 196 parts of methyl methacrylate, 4 parts of acrylic acid, 200 parts of methyl isobutyl ketone, octyl thioglycolate.
0 parts were added and heated to 100 ° C. under a nitrogen atmosphere. After 30 minutes, when the conversion reaches 3%, 300 parts of butyl acrylate, 175 parts of ethyl acrylate, and 2 parts of methacrylic acid 2
A mixture of 5 parts was dropped from the dropping funnel over 3 hours. Thereafter, polymerization was continued for 1 hour, and then 0.14 parts of methoxyphenol as a polymerization inhibitor was added to terminate the polymerization.

Volatile components were removed from the reaction solution using a twin screw extruder to obtain a milky white polymer. The polymer shows tackiness, Mn = 6.5 × 10 ⁴ , Mw / Mn = 2.6, T
g showed a wide value between -40 ° C and 80 ° C. The composition of the polymer thus obtained changed continuously, and its performance is shown in Table 3 as a comparative hot melt resin composition (5).

Comparative Example 6 2.0 parts of sodium methoxide and a hydrogenated rosin-based tackifier (the above-mentioned Fora) were added to 100 parts of the polymer having a continuously changing composition obtained in Comparative Example 4.
l 105), and kneaded under reduced pressure at 180 ° C for 1 hour. Obtained comparative hot melt resin composition (6)
The physical properties of are shown in Table 3.

Comparative Example 7 300 parts of butyl acetate were charged in the same apparatus as in Example 1, and 200 parts of vinyl acetate, 136 parts of butyl acrylate, 14 parts of 2-methacryloyloxyethyl acid phosphate, 335 parts of styrene, and acrylonitrile were used. A mixture consisting of 15 parts and 2.0 parts of octyl thioglycolate was placed in a dropping funnel. 200 parts were added from the dropping funnel and heated to 100 ° C. under a nitrogen atmosphere. Twenty minutes after the start of the polymerization, the mixture was dropped from the dropping funnel over 3 hours. After completion of the dropwise addition, polymerization was continued for 1 hour, and then 0.14 parts of methoxyphenol as a polymerization inhibitor was added to stop the polymerization.

To the reaction solution thus obtained, 3 parts of an antioxidant (Sumilizer BP101 described above) and 7 parts of zinc acetate were added and mixed, and volatile components were removed by a twin-screw extruder. The obtained polymer was fluorescent color transparent and Mn = 4.
5 × 10 ⁴ , Mw / Mn = 6.5, Tg = 42 ° C. The obtained polymer was used as a comparative hot melt resin composition (7), and the adhesive strength was shown in Table 4.

Comparative Example 8 300 parts of butyl acrylate, 175 parts of 2-ethylhexyl acrylate, 29 parts of acrylic acid, and 19 parts of methyl methacrylate were prepared in the same apparatus as in Example 1.
A 50% amount of the monomer mixture consisting of 6 parts was added, 740 parts of ethyl acetate and 1.5 parts of azobisisobutyronitrile were added, and polymerization was started at 70 ° C. under a nitrogen atmosphere. Twenty minutes after the start of the polymerization, dropping of the remaining monomer mixture was started and was completed in two hours. After completion of the dropwise addition, 1 part of azobisisobutyronitrile was charged, and polymerization was carried out for 1 hour. Then, 0.14 part of methoxyphenol was charged to terminate the polymerization.

The volatile components were removed from the thus obtained reaction solution using a twin screw extruder to obtain a transparent polymer. The polymer has a weak adhesive strength, Mn = 6.2 × 10
⁴ , Mw / Mn = 4.5, Tg = -11 ° C. This polymer was used as a comparative hot melt resin composition (8),
The adhesive properties are shown in Table 1.

Comparative Example 9 200 parts of styrene, 450 parts of butadiene and 25 parts of acrylic acid were added to the same apparatus as in Example 5.
, 25 parts of acrylonitrile and 1 part of octyl thioglycolate were added and heated to 140 ° C. Under these conditions,
After a polymerization reaction for 7 hours, volatile components were removed in the same manner as in Example 5 to obtain a polymer.

The polymer shows slight tackiness and Mn =
3.9 × 10 ⁴ , Mw / Mn = 3.9, Tg = −24 ° C.
Met. A tackifier (FTR6
100) and kneaded at 180 ° C. for 1 hour.
Table 2 shows the adhesive properties of the obtained comparative hot melt resin composition (9).

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

[Table 5]

[0135]

According to the first aspect, the hot melt resin composition of the present invention comprises a polyvalent mercaptan portion and a plurality of polymers having two or more different compositions radially extending from the polyvalent mercaptan portion. Part and 10,000-2
Since it contains a thermoplastic addition polymer having a number average molecular weight of 00000, it has excellent heat resistance and hot-melt workability, and is superior to conventionally known moisture-curable and energy ray-irradiable cross-linkable hot-melt resin compositions. Less time and equipment
Equivalent or almost equivalent heat resistance can be expressed by energy, and it is hard to cause a change over time in performance such as weather resistance.

The hot melt resin composition of the present invention comprises
According to the aspect, is a thermoplastic addition polymer having a polyvalent mercaptan portion and a plurality of polymer portions having two or more different compositions radially extending from the polyvalent mercaptan portion, wherein the polymer portion is The composition of each other has a gradient composition
Since it contains a thermoplastic addition polymer having a composition that changes, it has excellent heat resistance and hot melt workability, and is less than the conventionally known moisture-curable and energy-beam-irradiation-type crosslinkable hot-melt resin compositions. It can exhibit the same or almost the same heat resistance in terms of time, equipment, and energy, hardly causes a change in performance over time such as weather resistance, and is transparent.

The hot melt resin composition of the present invention has a third
According to the embodiment, a thermoplastic resin having a number average molecular weight of 10,000 to 200,000, having only one glass transition temperature peak having a width of 50 ° C. or more, and having a parallel light transmittance of 85% or more is provided. Because it contains a polymer, it is excellent in heat resistance and hot melt workability, and is equivalent or almost equivalent in less time, equipment and energy than the conventionally known moisture-curable and energy beam-irradiable cross-linkable hot melt resin compositions. Can exhibit heat resistance, does not easily change in performance over time such as weather resistance, and is transparent.

The hot melt resin composition of the present invention has a
According to the embodiment, in any one of the first embodiment to the third embodiment, the thermoplastic addition polymer is formed from a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. Since it is constituted, it is more excellent in heat resistance and weather resistance. According to a fifth aspect, the hot melt resin composition of the present invention includes a preparation step of preparing a mixture containing a first polymerizable unsaturated monomer and a polyvalent mercaptan; An addition step of adding a second polymerizable unsaturated monomer having a composition different from that of the polymerizable unsaturated monomer, and a first polymerizable unsaturated monomer and a second polymerizable group starting from a mercapto group of a polyvalent mercaptan. 2) a polymerization process for performing a radical polymerization of a polymerizable unsaturated monomer, and thus a thermoplastic addition polymer obtained by a production method, which is excellent in heat resistance and hot melt workability, and is conventionally known moisture curing. Mold and energy beam irradiation type cross-linkable hot melt resin composition, can develop the same or almost the same heat resistance with less time, equipment and energy than the cross-linkable hot melt resin composition, and hardly cause performance change such as weather resistance over time .

According to a sixth aspect of the hot melt resin composition of the present invention, in the fifth aspect, the production method comprises the steps of: starting from a mercapto group of a polyvalent mercaptan between the preparation step and the adding step; Since the method further includes a pre-polymerization step of performing radical polymerization of the polymerizable unsaturated monomer of 1, the method has an advantage that heat resistance and hot-melt workability are easily compatible.

The hot melt resin composition of the present invention has
According to the aspect, a preparation step of preparing a mixture containing a polymerizable unsaturated monomer comprising a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer and a polyvalent mercaptan, A polymerization step of radically polymerizing a polymerizable unsaturated monomer starting from the mercapto group of a polyvalent mercaptan as a starting point, thereby obtaining a thermoplastic addition polymer having a branched structure (star structure). Excellent heat resistance and hot melt workability, and exhibit equivalent or almost equivalent heat resistance in less time, equipment, and energy than conventionally known moisture-curable and energy-irradiation-type crosslinkable hot melt resin compositions. And it is hard to cause performance change with time such as weather resistance.

The hot melt resin composition of the present invention has
According to the aspect, in any one of the first aspect to the seventh aspect, a metal ion source is further included, so that the thermoplastic addition polymer is crosslinked with metal ions, so that the cohesive force is increased. Has further. According to the ninth aspect, the hot melt resin composition of the present invention according to the eighth aspect further includes a phosphate ester, so that the phosphate ester coordinates to the metal ion, so that the carboxyl group and the metal ion Has the further advantage that the bonding force of the resin decreases and the hot melt workability improves.

The hot melt resin composition of the present invention comprises
According to an embodiment, a (meth) acrylic thermoplastic addition polymer containing a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit, a metal ion source, and phosphoric acid Since it contains an ester, it has excellent heat resistance and hot melt workability, and is equivalent or almost equivalent in less time, equipment, and energy than conventionally known moisture-curable and energy ray-irradiable cross-linkable hot melt resin compositions. , And is unlikely to change over time in performance such as weather resistance.

The hot melt resin composition of the present invention comprises
According to one aspect, in any one of the first to tenth aspects, the composition further includes a tackifier resin, so that the viscosity is lower or the cohesive strength is further increased. . According to the twelfth aspect, the hot melt resin composition of the present invention is characterized in that, from the first aspect, the first
In any one of the first to fourth aspects, the composition further includes a wax, and thus has an advantage of lower viscosity.

Claims (12)

(57) [Claims] 1. A polyvalent mercaptan having a mercapto group
It has a polyvalent mercaptan portion , which is a remaining portion where protons are dissociated, and a plurality of polymer portions having two or more different compositions, wherein the polymer portion is the polyvalent mercaptan portion.
From the polyvalent mercury, one end of which has a carbon atom
Bonds to sulfur atoms derived from the mercapto group of the captan moiety
A hot melt resin composition having a combined structure and comprising a thermoplastic addition polymer having a number average molecular weight of 10,000 to 200,000. 2. The composition according to claim 1, wherein the plurality of polymer portions have a composition that is different from each other.
2. The hot melt resin composition according to claim 1, having a composition that varies with the composition. 3. A thermoplastic weight having a number average molecular weight of 10,000 to 200,000, a single glass transition temperature peak having a width of 50 ° C. or more, and a parallel light transmittance of 85% or more. A hot-melt resin composition containing a coalescence. 4. The method according to claim 1, wherein the thermoplastic addition polymer comprises a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit. The hot melt resin composition according to the above. 5. A preparation step of preparing a mixture containing a first polymerizable unsaturated monomer and a polyvalent mercaptan, and the mixture having a composition different from that of the first polymerizable unsaturated monomer. An adding step of adding a second polymerizable unsaturated monomer having the first polymerizable unsaturated monomer and the second polymerizable unsaturated monomer starting from a mercapto group of the polyvalent mercaptan A hot melt resin composition containing a thermoplastic addition polymer obtained by a production method including a polymerization step of performing radical polymerization of 6. The method according to claim 1, wherein the prepolymerization is carried out between the preparation step and the addition step, wherein a radical polymerization of the first polymerizable unsaturated monomer is carried out starting from a mercapto group of the polyvalent mercaptan. The hot melt resin composition according to claim 5, further comprising a step. 7. A preparing step of preparing a mixture containing a polymerizable unsaturated monomer comprising a carboxyl group-containing polymerizable unsaturated monomer and a (meth) acrylate monomer and a polyvalent mercaptan; A polymerization step of performing radical polymerization of the polymerizable unsaturated monomer starting from a mercapto group of a polyvalent mercaptan,
A hot melt resin composition containing a thermoplastic addition polymer having a branched structure obtained by a production method comprising: 8. The hot melt resin composition according to claim 1, further comprising a metal ion source. 9. The hot melt resin composition according to claim 8, further comprising a phosphate ester. 10. A (meth) acrylic thermoplastic addition polymer containing a carboxyl group-containing polymerizable unsaturated monomer unit and a (meth) acrylate monomer unit, a metal ion source, and a phosphate ester. And a hot melt resin composition comprising: 11. The hot melt resin composition according to claim 1, further comprising a tackifier resin. 12. The method according to claim 1, further comprising a wax.
2. The hot melt resin composition according to any one of 1 to 1.