JP4998767B2 - Method for producing acrylic polymer composition, adhesive / adhesive containing acrylic polymer composition obtained by the production method, and active energy ray-curable resin composition - Google Patents

Description

The present invention relates to a method for producing a A acrylic-based polymer composition, an acrylic polymer tacky adhesive comprising the composition as well as the radiation-curable resin composition obtained by the production method.

In order to improve the performance of a sticky / adhesive, a tackifier is widely added to the sticky / adhesive. As the tackifier, rosin resin, petroleum resin, terpene resin, etc. are often used.In particular, acrylic adhesives and adhesives have good compatibility with acrylic resins, and rosin resins are used. It is preferably used.

By the way, in recent years, interest in the environment has been increasing, and a sticky / adhesive that does not contain a volatile organic compound (VOC) and a water-based sticky / adhesive have been eagerly desired. Examples of the water-based adhesive / adhesive include those using an aqueous resin and those using an emulsion. However, an aqueous resin has a problem in water resistance, and thus an emulsion tends to be widely used.

However, the adhesives obtained by making conventional rosin resins into emulsions and adding them to acrylic polymer compositions have a decrease in water resistance, which is thought to be due to the use of emulsifiers, and whitening due to the ingress of water. A problem sometimes occurred.
In addition, in this method, it is necessary to prepare the acrylic resin and the tackifier resin emulsion separately, and thus there is a problem that productivity is poor. Therefore, in recent years, a method of preparing an acrylic resin in the presence of a tackifying resin and preparing an acrylic adhesive / adhesive in one step (pre-addition method) has been performed. When the acrylic resin is prepared in the presence of the above, it is difficult to increase the molecular weight of the acrylic resin. As a result, there is a problem that the cohesive force is insufficient and the performance as an adhesive / adhesive is adversely affected.
Therefore, the present applicant considers that the double bond existing in the rosin which is a tackifying resin is the cause of polymerization inhibition, and by controlling the content of tetrahydroabietic acid, a tackifying resin having a small polymerization inhibition property is obtained. In view of the above, an acrylic adhesive / adhesive composition using the tackifying resin was proposed (see Patent Document 1), but further improvement has been demanded.
JP 2000-327708 A

The present invention makes it possible to increase the molecular weight of an acrylic polymer with almost no polymerization inhibition even when it is used for the production of an acrylic polymer composition by a pre-addition method. Provide an acrylic polymer composition and an active energy ray-curable resin composition suitable as a tackifier and a tackifier / adhesive capable of imparting excellent properties such as water resistance and water resistance (whitening resistance). With the goal.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific rosin resin, and have completed the present invention.
That is, the present invention has a softening point of 120 to 180 ° C. obtained by reacting at least one selected from the group consisting of acrylic acid-modified rosin, acrylic acid-modified rosin disproportionate and acrylic acid-modified rosin hydride with a polyol. A method for producing an acrylic polymer composition characterized by polymerizing an acrylic monomer in the presence of a tackifier containing an rosin resin having an acid value of 1 to 15 ; and radiation-curable resin composition containing the tackifier and acrylic monomers, relates.

Since the tackifier of the present invention hardly causes polymerization inhibition even when present in the polymerization system of acrylic monomers, the acrylic polymer composition of the pre-addition method that can be manufactured with simpler manufacturing equipment and processes. It can be prepared. Further, the obtained acrylic polymer composition is excellent in adhesive and adhesive properties such as holding power to polyolefin, peel strength, tackiness, etc., and is suitable as an adhesive, but is also suitable as a binder for ink, paint, etc. .

The tackifier of the present invention is a resin obtained by reacting at least one selected from the group consisting of acrylic acid-modified rosin, acrylic acid-modified rosin disproportionate and acrylic acid-modified rosin hydride with a polyol, It contains a rosin resin having a softening point of 120 to 180 ° C. and an acid value of 1 to 15.
Acrylic acid-modified rosin is obtained by adding Diels-Alder to acrylic acid in a raw material rosin. Examples of the raw material rosin used for the production of acrylic acid-modified rosin include gum rosin, wood rosin, tall oil rosin and the like. In addition, although raw material rosin may be used as it is, it is preferable to use what was refine | purified by means, such as distillation, since the color tone of resin obtained can be made favorable. The method for reacting acrylic acid with Diels-Alder reaction is not particularly limited, and a known method can be adopted. Specifically, for example, acrylic acid is added at a rate of about 2 to 80 mol%, preferably 12 to 77 mol%, with respect to the raw material rosin, and the reaction is performed at about 180 to 240 ° C. for about 1 to 6 hours. You can do it. The acrylic acid modification rate of the acrylic acid modified rosin (ratio of acrylic acid modified rosin to the total rosin content in the sample (% by weight)) is the same as the polyol used in esterification to obtain a tackifier. An appropriate value may be set depending on the combination and the like, but it is usually adjusted to be in the range of 20 to 65%.

The acrylic acid-modified rosin disproportionate and the acrylic acid-modified rosin hydride in the present invention are obtained by further subjecting an acrylic acid-modified rosin to a disproportionation reaction and a hydrogenation reaction, respectively. These are preferable because they have better color tone than acrylic acid-modified rosin, and by using these resins as raw materials, the resins obtained are also light in color. In the hydrogenation or disproportionation reaction, the reaction conditions are not particularly limited, and any of them may be appropriately selected from known conditions.
The disproportionation reaction of the acrylic acid-modified rosin may be performed, for example, by heating the acrylic acid-modified rosin in an inert gas stream in the presence of a disproportionation catalyst. Examples of the disproportionation catalyst include supported catalysts such as palladium carbon, rhodium carbon, and platinum carbon, metal powders such as nickel and platinum, and iodides such as iodine and iron iodide. On the other hand, it is usually about 0.01 to 5% by weight, preferably about 0.01 to 1.0% by weight. The heating temperature is usually about 180 to 280 ° C., and the reaction time may be about 1 to 6 hours. Further, the disproportionation reaction of the acrylic acid-modified rosin can be performed simultaneously with the esterification described later. The simultaneous disproportionation reaction with the ester reaction is preferable in that the production process can be simplified.
The acrylic acid-modified rosin is hydrogenated in the presence of a hydrogenation catalyst in the presence of a hydrogenation catalyst in an airtight container having a hydrogen initial pressure of about normal pressure to 25 MPa and about 100 to 300 ° C., preferably 150 to 250. What is necessary is just to heat by heating. Here, as the hydrogenation catalyst, various known catalysts shown in the example of the disproportionation catalyst can be employed without any particular limitation, and the amount of the catalyst used is 0.01 to 5% by weight based on the addition reaction product. The reaction time is preferably about 0.05 to 3% by weight and the reaction time is about 1 to 6 hours. In the hydrogenation reaction, an alicyclic hydrocarbon solvent such as cyclohexane or decalin, or an aromatic hydrocarbon solvent such as toluene or xylene can be appropriately used.
The degree of disproportionation or hydrogenation of acrylic acid-modified rosin disproportionate or acrylic acid-modified rosin hydride is not particularly limited, but from the viewpoint of color tone, unmodified rosin in acrylic acid-modified rosin is as little as possible. Although it is preferable to be leveled or hydrogenated, generally, the degree of disproportionation is about 10 to 60% by weight of the dehydroabietic acid content to the total rosin content, and the degree of hydrogenation is about total rosin. The ratio of the total amount of dihydroabietic acid and tetrahydroabietic acid to the content is in the range of about 18 to 54% by weight.

The tackifier of the present invention comprises a rosin resin synthesized by esterifying the above-mentioned acrylic acid-modified rosin or the like with a polyol.

It does not specifically limit as a polyol used for the synthesis | combination of the rosin-type resin of this invention, A well-known thing can be used widely. Specifically, for example, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, and neopentyl glycol; trihydric alcohols such as glycerin, trimethylol ethane, and trimethylol propane; pentaerythritol, diglycerin, and the like Tetravalent alcohol; hexavalent alcohol such as dipentaerythritol. Among these, it is preferable to use a divalent alcohol, a trivalent alcohol, or a tetravalent alcohol in that an appropriate branched structure desirable as a tackifier can be formed in the obtained rosin resin, and in particular. It is preferable to use at least one selected from the group consisting of glycerin, pentaerythritol and dihydric alcohol. Furthermore, by using these in combination, the rosin-based resin obtained has a high softening point and a large molecular weight, and can have high tackifying properties such as adhesion and holding power.

As the reaction between acrylic acid-modified rosin and the like and polyol, a known esterification method of rosin and polyol can be employed. Specifically, for example, acrylic acid-modified rosin or the like and polyol are heated to about 150 to 300 ° C. under normal pressure to remove reaction product water out of the system. The charging ratio between the acrylic acid-modified rosin and the polyol and the polyol is not particularly limited, but usually the amount of the polyol having a hydroxyl group of about 1.0 to 1.5 times equivalent to the carboxyl group equivalent of the acrylic acid-modified rosin or the like. It is preferable to use it.
In the reaction, an esterification catalyst is not necessarily required. However, in order to shorten the reaction time, for example, an acid catalyst such as acetic acid or paratoluenesulfonic acid, an alkali metal hydroxide such as lithium hydroxide, a hydroxide Commonly known catalysts such as alkali earth metal hydroxides such as calcium and metal oxides such as calcium oxide and magnesium oxide can also be used.

  The rosin resin contained in the tackifier of the present invention has a softening point of 120 to 180 ° C. and an acid value of 1 to 15. By making the softening point and acid value of the rosin resin within these ranges respectively, the compatibility with the acrylic polymer that is the main component of the adhesive / adhesive is good, and the tackifier is contained. The resulting sticky / adhesive has high cohesive strength and can be excellent in sticky / adhesive properties. When the softening point of the rosin resin is less than 120 ° C., the cohesive force of the adhesive / adhesive obtained using the resin deteriorates, and when the softening point of the rosin resin exceeds 180 ° C., it becomes difficult to dissolve in acrylic monomers and solvents. Therefore, the handleability and workability are poor, and a good adhesive / adhesive cannot be obtained. In addition, since the acid value of the rosin-based resin is higher than 15, it exhibits a high polarity, so the compatibility with the acrylic polymer is deteriorated, and it is difficult to polymerize it. I can't get it.

Furthermore, it is preferable that the rosin resin has a repeating unit of a resin having a structure represented by the general formula (1) or the general formula (2) as a main component. The rosin resin thus obtained has a low polymerization inhibitory property even if a double bond generated by the Diels-Alder reaction is present in the molecule. The cause of this is not clear, but due to the steric hindrance increased by the addition of acrylic acid to the isopropyl group present in the abietic acid skeleton, which is thought to be involved in polymerization inhibition, the active radical becomes inaccessible, resulting in polymerization inhibition. This is thought to be due to a reduction in the performance.

In addition, the rosin resin preferably has a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of about 1,000 to 50,000, particularly 2,000 to 30,000. preferable. When the weight average molecular weight of the rosin resin is less than 1,000, the acrylic polymer composition obtained by using the resin tends to have insufficient adhesive / adhesive properties. Since solubility becomes poor and it becomes difficult to dissolve in an acrylic monomer or solvent, the handling property is inferior and the tackiness tends to be insufficient.

  The tackiness / adhesion imparting agent of the present invention preferably has a color tone of 3 or less Gardner color. By adding the color tone of the tackifier / adhesion imparting agent to the Gardner color 3 or less, when added to the tackifier / adhesive, it is possible to maintain the light color of the entire adhesive / adhesive and not impair the appearance. Is more preferable. In order to make the color tone of the tackifier to be Gardner color 3 or less, use acrylic acid-modified rosin disproportionate or acrylic acid-modified rosin hydride as resin acid, or esterify when acrylic acid-modified rosin is esterified. It can be realized by performing a disproportionation treatment simultaneously with the reaction, and performing a disproportionation treatment or a hydrogenation treatment after esterification.

The tackifier of the present invention contains the rosin-based resin obtained as described above, but the rosin-based resin may be added to the rosin-based resin as necessary as long as the effect as the tackifier of the present invention is not impaired. Other additives and other known tackifiers may be appropriately blended.
The tackifier of the present invention can be used for various adhesives / adhesives and can improve their adhesiveness / adhesion performance, but in particular, it has good compatibility with acrylic polymers and retention. , An acrylic polymer composition, an active energy ray-curable resin composition containing an acrylic monomer, and the like.

The acrylic polymer composition of the present invention is characterized by containing the tackifier and an acrylic polymer.
What is necessary is just to select suitably as an acryl-type monomer used in order to obtain an acryl-type polymer according to the various uses with which an acryl-type polymer composition is provided. For example, when the acrylic polymer composition is used for an acrylic adhesive / adhesive, various known acrylic esters can be used. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, and the like. More than one species can be used in combination. Moreover, a small amount of acrylic acid can be used in combination with the acrylic ester for the purpose of imparting storage stability to the resulting emulsion. Furthermore, copolymerizable monomers such as vinyl acetate and styrene can be used in combination within a range that does not impair the viscosity and adhesive properties of the acrylate polymer of the present invention.

As a method for polymerizing the acrylic monomer, known methods such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization can be employed. In the polymerization reaction, a polymerization initiator may be used as necessary. As the polymerization initiator, a known one can be used, and in the case of heat polymerization, a thermal polymerization initiator such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile or the like may be used. In the case of polymerization, a photopolymerization initiator such as benzoin, benzoin methyl ether, or benzophenone may be used.

The weight average molecular weight of the acrylic polymer (polystyrene conversion value by gel permeation chromatography) is about 50,000 to 1,500,000, preferably 60,000 to 1,000,000, which is a balance between high cohesive force and adhesive handling properties. Is preferable in that it can be secured.

  Although the usage-amount of the acrylic polymer and tackifier in the acrylic polymer composition of this invention is not specifically limited, 2-40 weight of tackifying resin is normally with respect to 100 weight part of acrylic polymers (solid content). Parts, preferably 3 to 20 parts by weight. When the amount used is less than 2 parts by weight, the effect of improving the adhesive properties of the resulting acrylic polymer composition is hardly recognized, whereas when it exceeds 40 parts by weight, the viscosity / adhesion performance is lowered. There is a tendency.

It does not specifically limit as a method of manufacturing an acrylic polymer composition using the tackifier of this invention, A well-known method is applicable. That is, it is produced by polymerizing an acrylic monomer in the presence of the “post-addition method” in which an acrylic polymer obtained by polymerizing an acrylic monomer is blended and produced with a tackifier and in the presence of the tackifier. Any production method of “pre-addition method” can be adopted.
As the post-addition method, a method of blending the tackifier of the present invention and an acrylic polymer in a form dissolved in an organic solvent, an emulsification of the tackifier of the present invention by a known method, and an aqueous resin emulsion tackifier In addition, examples include a method of blending into an acrylic polymer emulsion, a method of blending the tackifier of the present invention and an acrylic polymer by hot melting in the absence of a solvent, and the like. As a pre-addition method, the tackifier and acrylic monomer of the present invention are dissolved in an organic solvent, dispersed in water, or blended in a solvent-free state, and in the presence of a polymerization initiator, activity such as heat and light is performed. Examples thereof include a method of polymerizing by applying energy rays, mechanical energy, etc. to obtain an acrylic polymer composition.
In particular, since the tackifier of the present invention has low polymerization inhibition, it produces an acrylic polymer composition with excellent adhesive / adhesive properties even by a pre-addition method that can be manufactured with simpler manufacturing equipment and processes. It has the advantage that it can manufacture efficiently.
As the polymerization method of the acrylic monomer in the pre-addition method, the same method as the polymerization of the acrylic monomer described above can be used. That is, in the presence of a tackifier, the acrylic monomer may be polymerized by a known method such as bulk polymerization, solution polymerization, dispersion polymerization, or emulsion polymerization. In the case of employing emulsion polymerization, the emulsifier according to the pre-addition method is compared with the post-addition method in which each of the acrylic polymer and the tackifier is mixed with the emulsifier and mixed to prepare a composition. The amount of use can be reduced. Thus, the obtained emulsion-type adhesive / adhesive has the advantage of being able to suppress the decrease in water resistance resulting from the use of the emulsifier and the whitening (decrease in water resistance) due to the ingress of moisture. It does not specifically limit as an emulsifier, A well-known thing can be used.

The acrylic polymer composition of the present invention can be used as it is as a sticky / adhesive and can improve the sticky / adhesive performance. Viscosity, antifoaming agent, antioxidant, UV absorber, water resistance, film-forming aid, antiseptic, rust inhibitor, pigment, dye, etc. It can also be used as an agent.
Furthermore, it is also possible to improve the cohesive force and heat resistance by using a cross-linking agent such as a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, and an epoxy resin. Various known tackifiers may be used in combination.

The active energy ray-curable resin composition of the present invention contains the tackifier and an acrylic monomer.
As the acrylic monomer used in the active energy ray-curable resin composition, the acrylic monomer used in the acrylic adhesive / adhesive described above can be used. In addition, when an ultraviolet ray is used as the active energy ray, it is necessary to add a photopolymerization initiator.

  It does not specifically limit as a photoinitiator to be used, A well-known thing can be used. For example, acetophenone photopolymerization initiators such as 4-phenoxydichloroacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin photopolymerization initiators such as benzoin and benzoin methyl ether, benzophenone and benzoyl Examples thereof include benzophenone-based photopolymerization initiators such as benzoic acid, and thioxanthone-based photopolymerization initiators such as thioxanthone and 2-chlorothioxanthone.

The addition ratio of the photopolymerization initiator may be appropriately determined depending on the type of the photopolymerization initiator, but is usually 0.001 to 10 parts by weight based on 100 parts by weight of the total amount of the tackifier and the acrylic monomer of the present invention. Part by weight More preferably, it is preferably about 0.01 to 5 parts by weight.
The active energy ray-curable resin composition of the present invention has a viscosity suitable for coating (usually, adjusted to 300 to 20,000 mPa · s ⁻¹ at room temperature for handling). %) And may be prepolymerized, and may be adjusted to the above viscosity by blending a thickening polymer and oligomer as appropriate.

Thickening polymers include acrylic polymers obtained by copolymerizing (meth) acrylic acid alkyl ester with acrylic acid, acrylamide, acrylonitrile, acryloylmorpholine, styrene-butadiene rubber (SBR), isoprene rubber, styrene-butadiene block copolymer A combination (SBS), an ethylene-vinyl acetate copolymer or the like can be used.

  The active energy ray-curable resin composition of the present invention thus obtained is applied to a substrate such as a film or a tape, and then irradiated with active energy rays and cured by a polymerization reaction, for example. In particular, it exhibits excellent adhesiveness even on difficult-to-adhere adherends such as polyolefins.

Photopolymerization with ultraviolet rays can be carried out by irradiating ultraviolet rays having an illuminance of 1 to 200 mW / cm ² at a wavelength of 300 to 400 nm with a light amount of 400 to 4,000 mJ / cm ² times.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
Example 1
Unrefined Chinese gum rosin having an acid value of 171 with a softening point of 74 ° C and a color tone (Gardner) of 6 is distilled under a vacuum of 4.0 kPa under a nitrogen seal and distilled at a distillation temperature of 195 ° C to less than 250 ° C. The fraction (main fraction) was collected and used as purified rosin.
The obtained purified rosin had an acid value of 176.3, a softening point of 89.0 ° C., a color tone (Gardner) of 1-2, and a yield of 86%.
Next, 100 parts by weight of the purified rosin and 12 parts by weight of acrylic acid are charged into a glass reaction vessel equipped with a thermometer, a stirrer, a water separator, and a nitrogen introduction tube, and the mixture is stirred under a nitrogen stream. Then, after reacting at 220 ° C. for 4 hours, unreacted substances were distilled off under reduced pressure to obtain acrylic acid-modified rosin. The acrylic acid modification rate of the acrylic acid modified rosin was 48% by weight.
Next, 100 parts by weight of the acrylic acid-modified rosin as the resin acid, 5.1 parts by weight of glycerin (GLY), and pentaerythritol (PE) 8 are used as the resin acid so that the hydroxyl value / carboxylic acid ratio = 1.0. 0.0 part by weight (in terms of molar ratio, GLY: PE = 50: 50) was charged into the container, and 0.3 part by weight of palladium carbon (5% Pd—C (water content 50%)) was added, and nitrogen was added. A disproportionation reaction was performed simultaneously with esterification at 265 ° C. for 10 hours under an air stream to obtain a rosin resin. The softening point of this resin was 157 ° C., the acid value was 13.5, and the color tone was 450 Hazen.

(Example 2, Example 3, Comparative Example 2)
In the preparation of the rosin resin of Example 1, the rosin resin was obtained in the same manner as in Example 1 except that the charging ratio (molar ratio) of glycerin (GLY) and pentaerythritol (PE) was changed to the description in Table 1. Was prepared. The properties of the rosin resin obtained as a result are shown in Table 1.

(Example 4)
A glass reaction vessel equipped with a thermometer, a stirrer, a water separator, and a nitrogen introduction tube was charged with 100 parts by weight of the purified rosin described in Example 1 and 15 parts by weight of acrylic acid, and this was placed under a nitrogen stream. After reacting at 220 ° C. for 4 hours with stirring, unreacted substances were distilled off under reduced pressure to obtain acrylic acid-modified rosin. The acrylic acid modification rate of the acrylic acid modified rosin was 60% by weight.
Next, 100 parts by weight of the acrylic acid-modified rosin as the resin acid, 13.3 parts by weight of glycerin (GLY), and triethylene glycol (TEG) as the resin acid so that the hydroxyl value / carboxylic acid ratio = 1.2 6.5 parts by weight (in terms of molar ratio, GLY: TEG = 11: 1) is charged into the container, and 0.3 parts by weight of palladium carbon (5% Pd—C (water content 50%)) is added, and nitrogen is added. A disproportionation reaction was carried out simultaneously with esterification in an air stream at 250 ° C. for 8 hours to obtain a rosin resin, and the properties of the rosin resin obtained as a result are shown in Table 1.

(Examples 5 to 11, Comparative Example 3, Comparative Example 4)
In the preparation of the rosin resin of Example 4, the rosin resin was prepared in the same manner as in Example 4 except that the type of polyol and the charged proportion (molar ratio) of the polyol were changed to those described in Table 1. . The properties of the rosin resin obtained as a result are shown in Table 1.

(Example 12)
100 parts by weight of acrylic acid-modified rosin obtained in the same manner as in Example 4 and 1 part by weight of palladium carbon (5% Pd-C (water content 50%)) were charged into a shaking autoclave to remove oxygen in the system. Thereafter, the inside of the system was pressurized to 9.8 MPa with hydrogen and subjected to a hydrogenation reaction at 220 ° C. for 3 hours to obtain an acrylic acid-modified rosin hydride having an acid value of 245.8, a softening point of 132.0 ° C., and a color tone of 80 Hazen. It was.
Subsequently, a rosin resin was prepared in the same manner as in Example 4 except that the polyol was replaced with glycerin. The characteristics of the obtained rosin resin are shown in Table 1.

(Example 13)
In the preparation of the rosin resin of Example 4, palladium carbon (5% Pd-C (water content 50%)) was not added, the polyol was replaced with glycerin, and esterification was performed without a disproportionation reaction. Except for this, a rosin resin was prepared in the same manner as in Example 4. The properties of the rosin resin obtained as a result are shown in Table 1.

(Comparative Example 1)
As the rosin resin, a commercially available disproportionated rosin ester (Pine Crystal KE-100, manufactured by Arakawa Chemical Industries, Ltd.) composed of an ester of an unmodified purified colorless rosin and glycerin was used.

(Comparative Example 5)
100 parts by weight of the purified rosin described in Example 1 and 3 parts by weight of fumaric acid were charged, and the reaction was performed at 205 ° C. for 2 hours while stirring the mixture in a nitrogen stream to obtain a partially fumarated modified rosin. Next, 11.3 parts by weight of pentaerythritol and 0.1 parts by weight of palladium carbon (5% Pd-C (water content 50%)) were added, and disproportionation was performed simultaneously with esterification at 250 ° C. for 2 hours. A resin was obtained.

(Comparative Example 6)
In the preparation of the rosin resin of Example 4, polymerized rosin (CP-140, manufactured by Takehira Hayashi Chemical Industry Co., Ltd.) was used as the resin acid, 11 parts by weight of glycerin was charged as the polyol, and palladium carbon (5% Pd-C (hydrous) A rosin resin was prepared in the same manner as in Example 4 except that esterification was carried out without adding a rate 50%)) and without performing a disproportionation reaction.

(Comparative Example 7)
As the rosin resin, a commercially available polymerized rosin ester (Pencel D-160, manufactured by Arakawa Chemical Industries, Ltd.) composed of an ester of polymerized rosin and pentaerythritol was used.

(Comparative Example 8)
The acrylic acid-modified rosin prepared in Example 4 was used as it was without esterification and disproportionation.

Below, the measuring method used for evaluation of the characteristic of rosin-type resin is shown.
(Softening point)
The measurement was performed according to the ring and ball method described in JIS K2871.

(Acid value)
The measurement was performed according to JIS K5400.

(Molecular weight)
Gel permeation chromatography (manufactured by Tosoh Corporation, HLC8120, column used: TSKgel SuperHM-L × 3, developing solvent: tetrahydrofuran), both sample and reference have a flow rate of 0.60 ml / min and a weight average molecular weight at a measurement temperature of 40 ° C. Was measured as a polystyrene equivalent value.

(Color tone)
The Gardner color number was measured according to JIS K5400, and the Hazen color number was measured according to ASTM D1209.

(Acrylic acid modification rate)
Gel permeation chromatography (Tosoh Corporation, HLC8220GPC, columns used: Tosoh Corporation G2000HXL, G1000HXL, developing solvent: tetrahydrofuran), flow rate 1.00 ml / min (sample), 0.35 ml / min (reference), measurement temperature The acrylic acid modification rate was calculated based on the area ratio of the acrylic acid modified rosin peak to the total peak obtained.

Using the rosin resin prepared in the above Examples and Comparative Examples as a tackifier, an emulsion type acrylic polymer composition was prepared by a pre-addition method, and the adhesive performance was evaluated. The details are described below, and the results are shown in Table 2.
As a reference example, an emulsion-type acrylic polymerization composition was prepared without adding a tackifier, and its adhesiveness performance was evaluated.

  In a separable four-necked flask equipped with a thermometer, a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, (1) and (2) described in Table 2 were charged, while nitrogen bubbling and stirring (4) 21.4 parts by weight of water was added dropwise successively. The obtained mixture was dispersed by ultrasonic irradiation while stirring to obtain a monomer emulsion. Next, 16.3 parts by weight of water was charged in a separable four-necked flask similar to the above, heated to 80 ° C. under a nitrogen gas stream, and 0.075 parts by weight of (3) was added and dissolved. Subsequently, the monomer emulsion and 0.45 part by weight of (3) were dropped and polymerized over 3 hours. After completion of the dropwise addition, the remaining 0.02 parts by weight of (3) was further charged in several portions while keeping the temperature for 1.5 hours, followed by polymerization. Then, it cooled, the ammonia component and water were added, and it adjusted so that a non-volatile component might be 60 weight% and pH = 7-8, and it filtered, and obtained the acrylic polymer composition. Further, as Reference Example 1, an acrylic polymer was prepared by polymerization in the same manner as described above without using a tackifier.

(Creation of sample film for performance evaluation)
The obtained acrylic emulsion was directly applied to a PET film having a thickness of 38 μm with an applicator for a thickness of 100 μm, and dried for 5 minutes in a circulating air dryer at 105 ° C. to prepare a sample film. The thickness of the sample film was 30 μm.
Evaluation of the adhesive / adhesive properties of the acrylic polymer composition was carried out by the following method.

(Molecular weight)
Gel permeation chromatography (manufactured by Tosoh Corporation, HLC8120, column used: TSKgel SuperHM-L × 3, developing solvent: tetrahydrofuran) is performed under conditions of a flow rate of 1.00 ml / min and a measurement temperature of 40 ° C. The weight average molecular weight was measured as a polystyrene equivalent value.

(Compatibility)
The adhesive film was irradiated with light of 500 nm, and the transmittance (% T) was measured.

(Holding power)
In accordance with PSTC-7 (creep method), a sample film (25 mm x 25 mm) is attached to a stainless steel plate, a 1 kg load is applied to the sample film at 60 ° C, and the time (h) until the sample film falls is measured. did.

(Adhesive strength)
A sample film (length 150 mm x width 25 mm) is attached to a polypropylene plate (PE) and a stainless steel plate (SUS), respectively, and peeled off in the tape length direction of 180 ° at a peeling speed of 300 mm / min in accordance with PSTC-1. Then, the adhesive force (g / 25 mm) per 25 mm tape width was measured.

(Tackiness)
The ball tack test was conducted according to the method described in JIS Z 0237. By the DOW method, the sample was rolled on the adhesive surface of the sample film on a runway with an angle of 30 ° and a distance of 10 cm, and the maximum number of balls stopped within 10 cm of the sample film length was obtained.
The probe tack test was performed in accordance with ASTM D-2979, using an NS probe tack tester, polishing probe AA # 40, load 100 g / cm ² , dwell time 1 second.

Next, using the rosin resin prepared in the above examples and comparative examples as a tackifier, a solvent-type acrylic polymer composition was prepared by a pre-addition method, and the adhesive performance was evaluated. The details are described below, and the results are shown in Table 5.

In a separable four-necked flask equipped with a thermometer, a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, (3) described in Table 4 was charged, and the temperature was raised to 80 ° C. under a nitrogen stream. Subsequently, the mixed solution of (1) and (2) was dripped over 3 hours. Then, it kept at 80 degreeC for 2 hours, (4) was added and it cooled, and the acrylic polymer composition was obtained.

(Creation of sample film for performance evaluation)
The obtained acrylic polymer was directly applied to a 38 μm thick PET film with a 100 μm applicator and dried in a circulating air dryer at 105 ° C. for 5 minutes to prepare an adhesive film. The thickness of the adhesive film was 30 μm.

(Performance evaluation method)
The performance evaluation method for the adhesive / adhesive properties is the same as that for the emulsion type acrylic polymer composition.

Next, using the rosin resin prepared in the above Examples and Comparative Examples as a tackifier, an ultraviolet curable acrylic polymer composition was prepared by a pre-addition method, and the polymerization inhibition property was evaluated. The results are shown in Table 7.

(1) to (4) shown in Table 6 were mixed, and the obtained solution was dropped on a glass plate, and a polycarbonate film was covered thereon to a film thickness of 200 μm, and a 120 W high-pressure mercury lamp with oxygen blocked. An acrylic polymer was prepared by performing irradiation 10 times with an irradiation amount of 80 mJ / cm ² . As Reference Example 2, an acrylic polymer was prepared in the same manner without blending a rosin resin. As a result, as shown in Table 7, the adhesive property of the acrylic polymer obtained by mixing the tackifier of the present invention is higher than that of the comparative example. The tackifier of the present invention was confirmed to have very low polymerization inhibition.
The measurement of the molecular weight is the same as in the case of the emulsion type acrylic polymer composition.

Claims (7)

Softening point obtained by reacting at least one selected from the group consisting of acrylic acid-modified rosin, acrylic acid-modified rosin disproportionate and acrylic acid-modified rosin hydride with polyol is 120 to 180 ° C., and acid value is 1 to 1. 15. A method for producing an acrylic polymer composition, comprising polymerizing an acrylic monomer in the presence of a tackifier containing a rosin resin of 15. 2. The acrylic polymer composition according to claim 1, wherein the rosin resin is mainly composed of a repeating unit of a resin having a structure represented by the following general formula (1) or general formula (2) in the molecule. Manufacturing method .
General formula (1)

General formula (2)
The method for producing an acrylic polymer composition according to claim 1 or 2, wherein the rosin resin has a weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of 1,000 to 50,000. The method for producing an acrylic polymer composition according to any one of claims 1 to 3 , wherein the color tone of the tackifier is 3 or less Gardner color. The polyol in the rosin resin is at least one selected from the group consisting of a divalent alcohol, a trivalent alcohol, and a tetravalent alcohol . Production of an acrylic polymer composition according to any one of claims 1 to 4 Way . A pressure-sensitive adhesive composition containing an acrylic polymer composition obtained by the method for producing an acrylic polymer composition according to claim 1. Softening point obtained by reacting at least one selected from the group consisting of acrylic acid-modified rosin, acrylic acid-modified rosin disproportionate and acrylic acid-modified rosin hydride with polyol is 120 to 180 ° C., and acid value is 1 to 1. An active energy ray-curable resin composition containing a tackifier and an acrylic monomer , wherein the rosin resin is 15 .