KR20100087630A - Tackifier, adherence adhesive, acrylic adherence adhesive and radiation curable acrylic adherence adhesive - Google Patents

Abstract

PURPOSE: A tackifier, an adhesive composition, an acrylic adhesive composition, and an acrylic active energy ray cure type adhesive composition are provided to prevent the bromination of an adhesive even when the adhesive is exposed to the irradiation of ultraviolet ray for a long time and to obtain good miscibility with various acrylic polymers. CONSTITUTION: A tackifier contains rosin esters. The rosin esters have maximum absorbance A less than 0.15 in a range of more than 254nm. The content having a molecular weight of 320 is more than 95% of the total amount of a component having a molecular weight of 314-320. The tackifier has tint less than 300 Hazen and an acid value of 70-110 °C. The tackifier has a hydroxyl value of 0-60 mgKOH/g.

Description

Tackifier, adhesive agent composition, acrylic adhesive agent composition, acrylic active energy ray hardening type adhesive agent {TACKIFIER, ADHERENCE ADHESIVE, ACRYLIC ADHERENCE ADHESIVE AND RADIATION CURABLE ACRYLIC ADHERENCE ADHESIVE}

The present invention relates to a tackifier, a point-adhesive composition, an acrylic point-adhesive composition, and an acrylic active energy ray-curable point-adhesive composition.

Conventionally, rosin ester is used for various uses, such as tackifying resin for a point adhesive. Rosin esters are the reaction products of rosins and alcohols. Since rosin is made from rosin and the like, it contains various impurities. In addition, abietic acid, the main component of rosin, has a double bond in its molecule. Since these are considered to be the cause of deterioration with time and polymerization inhibition, radical improvement has been required.

By using disproportionated rosin or hydrogenated rosin which is excellent in stability as rosin, the above-mentioned fault can be solved to some extent. However, even with this method, deterioration with time and polymerization inhibition could not be satisfied.

Thus, the present applicant has proposed a rosin ester containing 50% by weight or more of tetrahydro abietic acid (see Patent Document 1). When this rosin ester is used, the fall of the weather resistance of a point and adhesive agent can be suppressed. However, when exposed to ultraviolet rays for a long time, the point-adhesive yellowed and the adhesive embrittleed, resulting in a problem of tack or adhesion deterioration.

By the way, in recent years, the manufacturing method of the acryl-type point adhesive agent which does not contain a solvent by superposing | polymerizing the acryl monomer which added the tackifier is proposed, for example, because of reduction of an environmental load (for example, a patent document) 2). However, in the said method, since a tackifier exists in a polymerization system, there exists a possibility that it may adversely affect a polymerization reaction. Therefore, the value obtained by dividing the detection output of the ultraviolet spectrometer detector at 254 nm in gel permeation chromatography (GPC) by the detection output of standard polystyrene is set to the polymerization inhibition parameter α, and the α is 1.0 or less, so that the UV polymerization rate is high. The method of obtaining curable acrylic adhesive is proposed (refer patent document 3).

However, the above method was also insufficient to suppress the molecular weight decrease of the acrylic polymer due to polymerization inhibition, resulting in a decrease in the cohesive force. Moreover, there existed a problem that compatibility with acrylic polymer worsened according to the kind of resin, and the balance of adhesion performance worsened.

Japanese Patent Laid-Open No. 11-335654 United States Patent No. 4175175 Japanese Patent Laid-Open No. 2003-277695

The present invention does not generate yellowing or embrittlement of the point and adhesive even when exposed to ultraviolet irradiation for a long time, and has good compatibility with various acrylic polymers, a point and adhesive composition, an acrylic point and adhesive composition, and an acrylic activity. It is an object to provide an energy ray-curable point and adhesive composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said subject can be solved by controlling the specific component amount contained in rosin, and making the ultraviolet absorbance of rosin ester below a fixed level. To complete.

In other words, the present invention has a maximum absorbance A (measurement condition: sample concentration 1 g / dm ³ , cell length 1 cm) in the region of 254 nm or more by ultraviolet absorption spectroscopy, 0.15 or less, gas chromatograph mass in the methylated product of the hydrolyzate A tackifier characterized in that the content of the component having a molecular weight of 320 is 95% or more of the total amount of the components having a molecular weight of 314 to 320 measured by the analysis; Point adhesive agent containing the said tackifier; Acrylic type adhesive agent containing the said tackifier; The present invention relates to an acrylic active energy ray-curable point-and-adhesive composition containing the tackifier.

Since the tackifier of this invention is favorable in light resistance, it is suitable as a tackifier of the point and adhesive for optical members. Moreover, since the tackifier of this invention has low polymerization inhibitory property, it is preferable as a tackifier of an active-energy-ray-curable acryl-type point adhesive, and especially for an optical member and legendary material which an active energy-ray-curable acryl-based point adhesive is effective. It can be used for adhesives and adhesives.

The tackifier of the present invention has a maximum absorbance A (measurement condition: sample concentration of 1 g / dm ³ , cell length of 1 cm) in a region of 254 nm or more by ultraviolet light absorbance method, and has a hydrolyzate ( Rosin esters containing 95% or more of the total amount of the components having a molecular weight of 314 to 320 as the content of the components having a molecular weight of 320 measured by gas chromatograph mass spectrometry in the methylated product of the aqueous solution. I) (A) (hereinafter referred to as component (A)).

Component (A) has a maximum absorbance A (measurement condition: sample concentration of 1 g / dm ³ , cell length of 1 cm) in a region of 254 nm or more by ultraviolet absorption spectroscopy, and is 0.15 or less, and is a gas chromatograph in the methylated product of the hydrolyzate. If content of the component of molecular weight 320 measured by mass spectrometry is 95% or more of the total amount of the component of molecular weights 314-320, a well-known thing can be used without a restriction | limiting. In the methylated product of the hydrolyzate, when the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry is not 95% or more of the total amount of the components having a molecular weight of 314 to 320 or in a region of 254 nm or more by ultraviolet absorbance spectroscopy. When the maximum absorbance A exceeds 0.15, the light resistance is lowered, or the acrylic polymer obtained when applied to an acrylic active energy ray-curable point adhesive (acrylic active energy line formation adhesive) Since the reaction is inhibited, the effects of the present invention cannot be achieved.

In component (A), the absorbance in the region of 254 nm or more by the ultraviolet absorbance method is mainly a peak related to carbon-carbon unsaturated bonds. Larger value means more unsaturated bonds in the molecule. In addition, it is thought that the said value becomes large when there are many coloring impurities. Since carbon-carbon unsaturated bonds are easily oxidized by ultraviolet rays or the like, they cause deterioration of color tone and embrittlement of the tackifier. In addition, carbon-carbon unsaturated bonds become a factor of polymerization inhibition in radical polymerization. Therefore, it is necessary to keep the said absorbance value low. In the methylated product of the hydrolyzate, the component having a molecular weight of 320 corresponds to that in which all of the unsaturated bonds in the molecule are hydrogenated among those in which the resin acid component derived from the rosin generated by the hydrolysis is methylated. In the methylated product of the hydrolyzate, the component having a molecular weight of 314 corresponds to having three carbon-carbon unsaturated bonds in the molecule. For this reason, the content of the component having a molecular weight of 320 being 95% or more of the total amount of the components having a molecular weight of 314 to 320 means that there are very few components having a carbon-carbon unsaturated bond contained in the component (A).

As the component (A), the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry in methylated products such as tetrahydro abietic acid and tetrahydro pimaric acid is usually measured. Rosin (a1) (henceforth component (a1)) containing 95% or more of the total amount of this molecular weight components 314-320 is made to react with alcohol (b) (henceforth component (b)). . In addition, rosin (a2) (henceforth a component (a2)) whose content of the component of molecular weight 320 measured by gas chromatograph mass spectrometry in less than 95% of the total amount of the component of molecular weights 314-320 measured in the methylation processed material is mentioned. 95% of the total amount of the component whose molecular weight is 314-320 measured by gas chromatograph mass spectrometry in the methylation process of a hydrolyzate by operation, such as hydrogenation, after making it react with component (b). You may make it ideal.

As component (a1), if content of the component of molecular weight 320 measured by gas chromatograph mass spectrometry in the said methylation processed material is rosin containing 95% or more of the total amount of components of molecular weight 314-320, it will specifically limit. A well-known thing can be used without it. As the component (a1), for example, tetrahydrobietic acid may be used alone. Moreover, you may prepare by mixing resin acid components, such as abiete acid, with tetrahydro abiete acid. Further, the component (a2) may be hydrogenated by a method described below so that the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry in the methylated product is 95% or more of the total amount of the components having a molecular weight of 314 to 320. good. Tetrahydrobietic acid can be obtained, for example, by the method described in Journal of Organic Chemistry 31, 4128 (1966), Journal of Organic Chemistry 34, 1550 (1969).

As the component (a2), natural rosins such as wood rosin, tall oil rosin, gum rosin and the like, disproportionated rosin, and hydrogenated rosin other than component (a1) Etc. can be mentioned.

As a specific example of component (b) used for manufacture of the tackifier of this invention, Monohydric alcohol, such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol; Dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol; Trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane; Tetrahydric alcohols such as pentaerythritol and diglycerin; Hexavalent alcohol, such as dipentaerythritol, etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, you may use glycidyl ether, glycidol, etc. as a component (b).

Among these, the use of a tetrahydric alcohol and / or a trihydric alcohol can make the softening point of the reaction product of the component (a1) or the component (a2) and the component (b) desired to be obtained at a desired temperature. It is preferable because of that. In addition, the usage-amount of a component (a1) or a component (a2), and a component (b) may be determined according to the target acid value and hydroxyl value of the reaction product to obtain, for example. Usually, it is preferable to make molar ratio (OH / COOH) of the carboxylic acid group in component (a1) or component (a2) and the hydroxyl group in component (b) about 0.5-2.

Component (A) can be obtained by esterifying component (a1) and component (b). The component (A) can also be obtained by hydrogenating the component (a2) and the component (b) after the esterification reaction. The esterification reaction can be carried out by a known esterification method. Specifically, it is made while removing the water produced | generated in high temperature conditions of about 150-300 degreeC out of a system. Moreover, when air mixes in esterification reaction, there exists a possibility that the produced | generated esterified product may color. It is preferable to perform esterification reaction under inert gas, such as nitrogen, helium, and argon. In the esterification reaction, an esterification catalyst may be used to shorten the reaction time. As the esterification catalyst, acid catalysts, hydroxides of alkali metals, metal oxides and the like can be used. Examples of the acid catalyst include acetic acid and para-toluene sulfonic acid. Calcium hydroxide etc. are mentioned as an alkali metal hydroxide. Examples of the metal oxides include calcium oxide and magnesium oxide.

A well-known method can be employ | adopted for hydrogenation of the reactant or component (a2) obtained by esterifying the component (a2) and the component (b). Hereinafter, the reactant or component (a2) obtained by esterifying the component (a2) and the component (b) may be a hydrogenation object. Hydrogenation is carried out by heating a hydrogenation object, for example, usually in the presence of a hydrogenation catalyst, usually about 1 to 25 MPa, preferably about 0.5 to 7 hours, preferably 1 to 5 hours, under hydrogen pressurization of 5 to 20 MPa. As a hydrogenation catalyst, various well-known things, such as a supported catalyst, a metal powder, and an iodide, can be used. Examples of the supported catalysts include palladium carbon, rhodium carbon, ruthenium carbon, platinum carbon and the like. Nickel, platinum, etc. are mentioned as a metal powder. Iodide, iron iodide, etc. are mentioned as iodide. Among them, palladium, rhodium, ruthenium or platinum-based catalysts are preferred in terms of hydrogenation efficiency (good hydrogenation rate, short hydrogenation time). The usage-amount of a hydrogenation catalyst is about 0.01-10 weight part normally with respect to 100 weight part of hydrogenation objects, Preferably it is 0.01-5 weight part. Moreover, hydrogenation temperature is about 100-300 degreeC, Preferably it is 150-290 degreeC. In addition, hydrogenation may be carried out in the state which melt | dissolved rosin in the solvent as needed. Although the solvent to be used is not specifically limited, What is necessary is just a solvent which is inert in reaction, and a raw material and a product are easy to melt | dissolve. As a solvent, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran (THF), dioxane, etc. can be used 1 type or in combination of 2 or more types, for example. Although the usage-amount of a solvent is not specifically limited, Usually, it is used so that solid content may be about 10 weight% or more with respect to raw material resin. Preferably it is 10 to 70 weight% of range.

In the case of the hydrogenated rosin ester hydrogenated under general hydrogenation conditions, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry in the methylated product of the hydrolyzate is 20% by weight of the total amount of the components having a molecular weight of 314 to 320. It only increases to a degree. Therefore, it is necessary to repeat the hydrogenation, increase the amount of catalyst used, and select an appropriate catalyst type for raising the hydrogenation temperature.

It is preferable that the softening point (circulation method) of the component (A) obtained by making it above is about 50-120 degreeC normally. Since the handling of a tackifier becomes easy by making a softening point 50 degreeC or more, it is preferable. Moreover, it is especially preferable to make a softening point 70-110 degreeC, an acid value 0-30 mgKOH / g, and a hydroxyl value 0-60 mgKOH / g, and a softening point 85-95 degreeC, and an acid value 2-2. It is most preferable that 12 mgKOH / g and hydroxyl value shall be 5-20 mgKOH / g. By making the color tone of component (A) colorless and transparent below 300 Hazen (JIS K 0071-1), it can be used suitably for the use of an optical member and a legendary material material where a color tone is important. .

Although the tackifier of this invention contains the said component (A), you may contain various additives, such as antioxidant, as needed.

The point and adhesive composition of this invention contain said tackifier. Although it does not specifically limit as a point adhesive agent, For example, an acryl-type adhesive agent composition, a styrene-conjugated diene type block copolymer adhesive composition, an ethylene-type hot melt adhesive composition (ethylene system hot melt 接着 劑 物 成 物) and the like.

The acrylic point adhesive agent of this invention contains said tackifier and acrylic polymer at least.

The acrylic monomer used in order to obtain an acrylic polymer can determine the composition suitably according to the various uses for which an acryl-type point adhesive agent is provided. Examples of the acrylic monomers include various acrylic esters and / or methacrylic acid esters (hereinafter referred to as (meth) acrylic acid esters). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. are mentioned, for example. Moreover, (meth) acrylic acid, (meth) acrylic acid glycidyl, (meth) acrylic acid 2-hydroxyethyl, N-methylol (meth) acrylamide, etc. are mentioned as said (meth) acrylic acid as a crosslinkable acrylic monomer. It can be used together with ester. If necessary, other copolymerizable monomers such as vinyl acetate, styrene, and the like may be used in combination so as not to impair the adhesive properties of the (meth) acrylic acid ester polymer. Moreover, as an acryl-type monomer, it is also possible to use the polymeric oligomer provided with the olefin double bond obtained by superposing | polymerizing at least 1 sort (s) of the said monomer.

As a polymerization method of the said acryl-type monomer, a well-known method, such as block polymerization, solution polymerization, dispersion polymerization, emulsion polymerization, can be employ | adopted without a restriction | limiting in particular. . Usually, as a polymerization initiator, thermal polymerization can be carried out by using thermal initiators such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile potassium persulfate, and ammonium persulfate. have. Moreover, you may superpose | polymerize by ultraviolet irradiation using the photoinitiator which consists of benzoin, benzoin methyl ether, and benzophenone. In addition, a redox initiator can be arbitrarily selected by a combination of electron beam irradiation, persulfate such as potassium persulfate, tertiary amine, thiourea, and the like. The solvent in solution polymerization is not specifically limited, The well-known solvent normally used for superposition | polymerization can be used. In particular, in the case of a solvent type acrylic polymer, a solvent can be selected according to a use. Toluene, ethyl acetate, etc. are mentioned specifically ,. The dispersing agent in dispersion polymerization can use a well-known thing without a restriction | limiting in particular. In addition, the emulsifier in emulsion polymerization is not specifically limited, Usually, what is used for normal emulsion polymerization, such as a well-known anionic emulsifier and a nonionic emulsifier, can be used.

It is preferable to make the usage-amount of the tackifier in the acryl-type adhesive agent of this invention into the range of about 2-40 weight part with respect to 100 weight part of acrylic monomers. It is preferable to set it as the range of 5-20 weight part especially. By setting it as 2-40 weight part, since strong adhesive force can be obtained and tack becomes favorable, it is preferable.

The molecular weight of the acrylic polymer obtained by the polymerization method is not particularly limited as long as there is sufficient cohesive force as the acrylic polymer composition. It is preferable to make polystyrene conversion value by) into 150,000 or more.

Moreover, it is also possible to further improve cohesion force and heat resistance by adding a crosslinking agent to the obtained acrylic polymer composition. As a crosslinking agent, a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, an epoxy resin, etc. are mentioned. It is preferable to use a polyisocyanate compound especially among these crosslinking agents. As a specific example of a polyisocyanate compound, 1, 6-hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 4, 4- diphenylmethane diisocyanate, etc. are mentioned. Can be. Moreover, a filler, antioxidant, a ultraviolet absorber, etc. can be used suitably for the acrylic point adhesive agent of this invention as needed. Moreover, it is also possible to use various well-known tackifying resin together with the acryl-type adhesive agent of this invention in the range which does not deviate from the objective of this invention.

The acrylic active energy ray hardening type adhesive agent of this invention contains at least the above-mentioned tackifier and the monomer used as a raw material of the said acrylic polymer. Moreover, you may add a crosslinking agent etc. to the said acrylic active energy ray hardening-type point adhesive agent as needed. It is preferable that the usage-amount of the component (A) in the acrylic active energy ray hardening-type adhesive agent of this invention shall be about 2-40 weight part with respect to 100 weight part of acrylic monomers, Especially 5-20 weight part It is preferable to set it as the range. By setting it as 2-40 weight part, since strong adhesive force can be obtained and tack becomes favorable, it is preferable.

The said acrylic active energy ray hardening type point-and-adhesive composition can be hardened by active energy rays, such as an ultraviolet-ray and an electron beam. The weight average molecular weight of the acrylic polymer obtained by hardening becomes about 50,000 or more normally.

Moreover, a filler, a plasticizer, a thickener, an antifoamer, and antioxidant to the said acrylic active energy ray hardening-type adhesive agent in the range which does not adversely affect a viscosity, adhesive performance, and sclerosis | hardenability. Various well-known additives, such as a ultraviolet absorber, a water-resistant agent, a film forming agent, a preservative, a rust inhibitor, a pigment, and a dye, may be contained suitably.

The styrene-conjugated diene block copolymer adhesive composition of this invention mix | blends the said tackifier, a styrene-conjugated diene block copolymer, and an oil.

The styrene-conjugated diene block copolymer is a block copolymer in which styrenes such as styrene and methyl styrene and conjugated dienes such as butadiene and isoprene are appropriately selected and copolymerized according to the purpose of use. Usually the weight ratio of styrenes / conjugated dienes is 10/90 to 50/50. As a specific example of such a block copolymer, SBS type block copolymer and styrene (S) / which have a weight ratio of styrene (S) / butadiene (B) in the range of 10/90-50/50 are for example. SIS type block copolymer etc. in which the weight ratio of isoprene (I) exists in the range of 10 / 90-30 / 70 is mentioned. The styrene-conjugated diene-based block copolymer of the present invention also includes a hydrogenated conjugated diene component of the block copolymer. Specific examples of the hydrogenated product include so-called SEBS-type block copolymers and SEPS-type block copolymers.

Examples of the oil include plasticizing oils such as naphthene-based oils, paraffinic oils and aromatic oils. Naphthenic oil and paraffinic oil are preferable at the point that the fall of cohesion force is small. Specifically, naphthene system process oil, paraffin process oil, liquid polybutene, etc. are mentioned.

As the usage-amount of each component, it is made to contain about 15-210 weight part of tackifiers, and about 4-200 weight part of oil with respect to 100 weight part of styrene-conjugated diene type block copolymers, for example.

When the tackifier is less than 15 parts by weight, the melt viscosity of the pressure-sensitive adhesive composition may increase, and when it exceeds 210 parts by weight, the holding force tends to be insufficient. Moreover, when oil is less than 4 weight part, the melt viscosity of an adhesive composition becomes high, and when it exceeds 200 weight part, a holding force may become inadequate.

Moreover, additives, such as a filler and antioxidant, can be further added to the styrene-conjugated diene type block copolymer adhesive composition of this invention as needed.

The ethylenic hot melt adhesive composition of the present invention can be obtained by blending the tackifier in an ethylene copolymer.

The ethylene copolymer can be used as a copolymer of ethylene and a monomer copolymerizable with ethylene, which has conventionally been used for a hot melt adhesive. As a monomer copolymerizable with ethylene, vinyl acetate etc. are mentioned, for example. Content of vinyl acetate is about 20 to 45 weight% normally. Moreover, it is preferable that melt index (190 degreeC, load 2160g, 10 minutes) is 10-400 g / 10min in molecular weight.

As a wax, what is used in a hot melt adhesive can be used. Specific examples of the wax include petroleum waxes such as paraffin wax and microcrystalline wax, synthetic waxes such as Fischer-Tropsch wax and low molecular weight polyethylene wax.

The ethylene-based hot melt adhesive of the present invention contains about 50 to 150 parts by weight of the tackifier of the present invention and about 10 to 100 parts by weight of wax based on 100 parts by weight of the ethylene copolymer. When the tackifier is 50 parts by weight or more, sufficient adhesive strength can be obtained, and when it exceeds 150 parts by weight, sufficient holding force may not be obtained. Moreover, when wax is less than 10 weight part, the melt viscosity of the adhesive composition which can be obtained becomes high too much, and when it exceeds 100 weight part, sufficient holding force may not be obtained. Moreover, additives, such as a filler and antioxidant, can be further added to the ethylenic hot melt adhesive agent of this invention as needed.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. In addition, unless otherwise indicated, "%" and "part" mean an "weight%" and a "weight part" in an Example.

Preparation Example 1 (Preparation of solvent type acrylic polymer)

50 parts of ethyl acetate was placed in a reactor equipped with a stirring device, a cooling tube, two dropping funnels, and a nitrogen inlet tube, and then heated up until the temperature in the system reached about 75 ° C. under a nitrogen stream. (Iii). Subsequently, a dropping funnel in which 48.5 parts of butyl acrylate, 48.5 parts of 2-ethylhexyl acrylate and 3 parts of acrylic acid were mixed in advance, and dropping into the system for about 2 hours from a dropping funnel containing 0.1 part of azobisisobutyronitrile and 30 parts of ethyl acetate ( Down), and maintained at the same temperature for 5 hours to complete the polymerization reaction. By adding ethyl acetate and adjusting the solid content to about 50%, a composition containing an acrylic polymer was obtained.

Preparation Example 2 (Preparation of Rosin Ester 1)

(First hydrogenation reaction)

200 g of Chinese hydrogenated rosin, 3 g of 5% palladium alumina powder (NE Chemcat Co., Ltd.) and 200 g of cyclohexane were added to a 1 liter autoclave, and after removing oxygen from the system, the system was pressurized to 6 MPa. Next, it heated up to 200 degreeC. After reaching the temperature, the system was repressurized to maintain 9 MPa, hydrogenated for 4 hours, the solvent was separated from the furnace, and then cyclohexane was removed under reduced pressure to obtain an acid value of 174 and a softening point of 79 ° C. 189 g of additional rosin was obtained.

(Esterification reaction)

Subsequently, 180 g of hydrogenated rosin was added to a reactor equipped with a stirring device, a cooling tube, and a nitrogen inlet tube, and melted to 200 ° C., followed by 21 g of glycerin and reacted at 280 ° C. for 10 hours. 175g of hydrogenated rosin esters which are softening point 90 degreeC and acid value 11 were obtained.

(Secondary hydrogenation reaction)

Into a 1 liter autoclave, 170 g of hydrogenated rosin ester, 1 g of 5% palladium carbon (50% water content) and 170 g of cyclohexane were added, and after removing oxygen in the system, the system was pressurized to 6 MPa. Next, it heated up to 200 degreeC. After reaching the temperature, the system was repressurized to maintain 9 MPa, hydrogenated for 4 hours, the solvent was separated from the furnace, and cyclohexane was removed under reduced pressure, and the rosin ester having an acid value of 10, a softening point of 92 ° C and a hydroxyl group of 18 was obtained. 164 g of 1 was obtained. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 100% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 200 halogen (H). In addition, in the softening point and the methylation process of the hydrolyzate, content, color tone, and acid value of the component of molecular weight 320 measured by gas chromatograph mass spectrometry were measured by the method mentioned later. In the following, these values are measured by the same method.

Preparation Example 3 (Preparation of Rosin Ester 2)

(First hydrogenation reaction)

191 g of rosin having an acid value of 175 and a softening point of 79 ° C was obtained in the same manner as in Production Example 2, except that the amount of the 5% palladium alumina powder was changed to 2 g and the hydrogenation reaction time was changed to 3 hours.

(Esterification reaction)

175 g of rosin ester having a softening point of 91 DEG C and an acid value of 12 was obtained in the same manner as in Production Example 2, except that 180 g of rosin having an acid value of 175 obtained by primary hydrogenation and a softening point of 79 DEG C was used.

(Secondary hydrogenation reaction)

163 g of rosin ester 2 having an acid value of 12, a softening point of 92 ° C. and a hydroxyl group of 18 was obtained in the same manner as in Production Example 2, except that 170 g of the softening point obtained by esterification and 170 g of the rosin ester having an acid value were used. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 99% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 200H.

Preparation Example 4 (Preparation of Rosin Ester 3)

(First hydrogenation reaction)

Except having changed the usage-amount of 5% palladium alumina powder to 1.5g, it carried out similarly to manufacture example 3, and obtained 194g of rosin with an acid value of 175 and a softening point of 78 degreeC.

(Esterification reaction)

175 g of rosin ester having a softening point of 90 DEG C and an acid value of 10 was obtained in the same manner as in Production Example 2, except that 180 g of rosin having an acid value of 175 obtained by primary hydrogenation and a softening point of 78 DEG C was used.

(Secondary hydrogenation reaction)

162 g of rosin ester 3 having an acid value of 9, a softening point of 91 ° C and a hydroxyl group of 15 was obtained in the same manner as in Production Example 2, except that 170 g of a rosin ester having a softening point of 90 ° C and an acid value of 10 was obtained by esterification. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 98% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 200H.

Preparation Example 5 (Preparation of Rosin Ester 4)

(First hydrogenation reaction)

200 g of hydrogenated rosin from China, 4 g of 5% palladium carbon (50% hydrous, manufactured by NE Chemcat Co., Ltd.) and 200 g of cyclohexane were added to a 1 liter autoclave, and after removing oxygen from the system, the system was pressurized to 6 MPa. Next, it heated up to 200 degreeC. After reaching the temperature, the inside of the system was repressurized to maintain 9 MPa, hydrogenated for 3 hours, the solvent was separated from the furnace, and then cyclohexane was removed under reduced pressure to obtain 190 g of rosin having an acid value of 172 and a softening point of 79 ° C.

(Esterification reaction)

Subsequently, 180 g of rosin was added to a reactor equipped with a stirring device, a cooling tube, and a nitrogen inlet tube and melted to 200 ° C., followed by 21 g of glycerin and reacted at 280 ° C. for 10 hours. 172g of rosin esters of the softening point 91 degreeC and acid value 9 were obtained.

(Secondary hydrogenation reaction)

170 g of the rosin ester obtained above, 1 g of 5% palladium carbon (50% water content), and 170 g of cyclohexane were added to a 1 liter autoclave. It was. After reaching the temperature, the system was repressurized to maintain 9 MPa, hydrogenated for 4 hours, the solvent was separated from the furnace, and cyclohexane was removed under reduced pressure, and the rosin ester having an acid value of 8, a softening point of 91 ° C and a hydroxyl group of 14 was obtained. 163 g of 4 was obtained. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 96% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 150H.

Preparation Example 6 (Preparation of Rosin Ester 5)

(First hydrogenation reaction)

Except having changed the usage-amount of 5% palladium carbon into 2 g, 190 g of rosin which has an acid value of 170 and a softening point of 80 degreeC was obtained like manufacture example 5.

(Esterification reaction)

172 g of rosin ester having a softening point of 90 DEG C and an acid value of 8 was obtained in the same manner as in Production Example 5, except that 180 g of rosin having an acid value of 170 obtained by primary hydrogenation and a softening point of 80 DEG C was used.

(Secondary hydrogenation reaction)

161 g of rosin ester 5 having an acid value 7, a softening point of 90 ° C. and a hydroxyl group of 16 was obtained in the same manner as in Production Example 5, except that 170 g of a rosin ester having a softening point of 90 ° C. and an acid value of 8 was used. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 94% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 150H.

Preparation Example 7 (Preparation of Rosin Ester 6)

300 g of rosin was added to a reactor equipped with a stirrer, a cooling tube, and a nitrogen inlet tube, and heated and melted to 200 ° C. Then, 33 g of glycerin was added and reacted at 280 ° C for 12 hours. 299 g of rosin esters having a softening point of 93 ° C and an acid value of 6 were obtained.

250 g of the rosin ester obtained above and 7.5 g of 5% palladium carbon (water content: 50%) were put into a 1 liter autoclave, and after removing oxygen in the system, the system was pressurized to 6 MPa and then heated to 240 ° C. After reaching the temperature, the inside of the system was repressurized to maintain 9 MPa, hydrogenated for 3 hours, the solvent was separated from the furnace, and 163 g of rosin ester 6 having an acid value of 6, a softening point of 88 ° C and a hydroxyl group of 14 was obtained. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 60% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 200H.

Preparation Example 8 (Preparation of rosin ester 7)

Except having made the usage-amount of 5% palladium carbon 2g, it carried out similarly to manufacture example 7, and obtained 164g of rosin esters 7 of acid value 6, 90 degreeC of softening point, and 12 hydroxyl groups. In the methylated product of the hydrolyzate, the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry was 20% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 300H.

(Softening point)

It measured by the round ball method of JISK2531.

(Quantification of the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry in the methylated product of the hydrolyzate)

The rosin esters obtained in Production Examples 2 to 8 were hydrolyzed (addition of potassium hydroxide in n-hexanol to reflux reaction for 2 hours, and then the resin acid obtained by neutralization with hydrochloric acid was used for analysis). Quantification was performed with a chromatograph mass spectrometer.

In the measurement, 0.1 g of the rosin ester obtained in the preparation example was dissolved in 2.0 g of n-hexanol, and 0.1 g of this solution and a 0.2 mol methanol solution of on-column methylating agent (phenyltrimethylammonium hydroxide (PTAH)) 0.4 g of GL Science was uniformly mixed and 1 µl was injected into gas chromatograph mass spectrometry (GC / MS). The peak area ratio of the component having a molecular weight of 320 to the total peak area of the components having a molecular weight of 314 to 320 was measured, and this was taken as the content of the component having a molecular weight of 320.

Device used

GC / MS: Gas Chromatograph Agilent 6890, Mass Spectrometer Agilent 5973, Column Advance-DS

(hue)

It measured in units of Hazen according to JIS K 0071-3.

(Acid value)

It measured by potentiometric titration according to JIS K 0700.

(Hydroxyl value)

It measured by potentiometric titration according to JIS K 0700.

(Absorbance)

25.0 mg of the rosin ester obtained in the production example was accurately weighed in a 25 ml volumetric flask, dissolved in cyclohexane, and defined to 25 ml of labeling line. Absorbance is measured with a UV spectrophotometer (HITACHI u-3210 spectrophotometer) using a 1 cm quartz cell. The maximum absorbance in the region above 254 nm could be read.

Example 1

A 50% ethyl acetate solution of the rosin ester 1 obtained in Preparation Example 2 was added to 80 parts of the solvent-type acrylic polymer obtained in Preparation Example 1, and a polyisocyanate compound (Nippon Polyurethane Co., Ltd. product, trade name "Coronate L") was used as a crosslinking agent. (CORONATE L) ") 2.5 parts were added, and the solvent type acrylic adhesive agent composition was obtained. The obtained solvent-type acrylic point adhesive agent is applied to a polyester film having a thickness of 38 μm with a die type applicator so that the dry film thickness is about 30 μm (coating width 25 mm), and then the point and adhesive agent After drying the solvent in a composition varnish for 5 minutes in a 105 degreeC ventilation drier, the sample tape was produced, and it solidified for 1 week under 23 degreeC65% RH conditions, and performed the light resistance test mentioned later. The results are shown in Table 2.

(Light resistance test)

Using a probe tack (NS probe tack tester, manufactured by Nichiban Co., Ltd.) before and after the sample tape was irradiated with a constant amount of accumulated light by a high pressure mercury lamp, and a load of 100 g / cm ² , The change in dwell time 1 second) was evaluated.

(Examples 2 to 4 and Comparative Examples 1 to 3)

A sample tape was prepared in the same manner as in Example 1 except that the rosin ester used in Example 1 was changed as shown in Table 1, and a light resistance test was performed. The results are shown in Table 2.

Table 1

[Table 2]

Example 5

The solvent type acrylic polymer obtained in Production Example 1 was dried in a 105 ° C. ventilator for 5 hours. To 24 parts by weight of the obtained acrylic polymer, 25 parts of 2-ethylhexyl acrylate, 25 parts of butyl acrylate, 6 parts of acrylic acid, and 20 parts of rosin ester 1 obtained in Production Example 2 were mixed, and a polyisocyanate compound (Nippon Poly) was used as a crosslinking agent. 2.5 parts of urethane high school products, brand name "Coronate L", and 0.2 parts of DAROCUR 1173 (made by Chiba Japan Co., Ltd.) as a photoinitiator are added to the active energy ray-curable pressure-sensitive adhesive composition Was prepared.

The obtained solvent type acrylic point adhesive agent was apply | coated to the polyester film of thickness 38micrometer by the die-type applicator so that dry film thickness might be about 30 micrometers (coating width 25mm), and ultraviolet-ray was irradiated and the sample tape was obtained.

(Adhesion)

According to the JIS Z 0237 method, the sample tape was pressed onto a polyethylene substrate, which is an adherend, by using a 2 kg rubber roller at a bonding area of 25 mm × 125 mm, and then left at 20 ° C. for 24 hours. It was. Thereafter, a 180 ° peel test was performed at 20 ° C. at a peel rate of 300 mm / min using a TENSILON tensile testing machine, and the adhesion force (N / 25 mm) per 25 mm in width was measured. The results are shown in Table 3.

(Static Load Peelability)

The sample tape was pressed onto the adherend polyethylene plate substrate using a 2 kg rubber roller with a bonding area of 25 mm x 100 mm, and then the 2 kg roll was reciprocated and bonded once, and 30 minutes later, a 50 g load was applied to the tape end. The polyethylene plate was fixed so that 90 degree peeling might be carried out, and the peeling distance per hour was measured in 23 degreeC atmosphere. In the case of total peeling within 1 hour, the time required was measured. The results are shown in Table 3.

Comparative Example 4

A sample tape was obtained in the same manner as in Example 5 except that the rosin ester 1 was not mixed in Example 5.

Table 3

Claims (7)

The maximum absorbance A (measurement condition: sample concentration 1g / dm ³ , cell length 1cm) in the region of 254nm or more by ultraviolet absorbance method is 0.15 or less, methylated product of the hydrolyzate Tackiness provision characterized in that the content of the component having a molecular weight of 320 measured by gas chromatograph mass spectrometry contains rosin ester (A) of 95% or more of the total amount of the components having a molecular weight of 314 to 320. Article (粘着 附 與 劑).
The method of claim 1,
Tint is 300 Hazen or less, Tackifier characterized by the above-mentioned.
The method according to claim 1 or 2,
A tackifier characterized by a softening point of 70 to 110 ° C, an acid value of 0 to 30 mgKOH / g, and a hydroxyl value of 0 to 60 mgKOH / g.
The method of claim 1,
The softening point is 85-95 degreeC, the acid value is 2-12 mgKOH / g, and the hydroxyl value is 5-20 mgKOH / g, The tackifier characterized by the above-mentioned.
The point adhesive agent containing the tackifier of Claim 1.
The acrylic point adhesive agent containing the tackifier of Claim 1.
Acrylic active energy ray hardening type | mold adhesive agent containing the tackifier of Claim 1 (acryl system active energy line formation adhesive composition).