JP5264826B2 - Acrylic adhesive manufacturing method - Google Patents

Description

The present invention relates to an acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape preferably used for adhesion and fixing of a member used in a closed space where odor is a problem in a vehicle, a house, etc., or an electronic device where volatile gas is a problem. And a vehicle air conditioner unit using the same.

In order to adhere and fix members, double-sided tapes are widely used in vehicles, houses, and even inside electronic devices. In recent years, however, several problems have been raised regarding the use of these adhesive tapes. For example, problems such as fogging due to high-boiling volatile components in glass inside automobiles, and malfunctioning of electronic devices due to high-boiling volatile components and impurities in members used inside electronic devices Is listed. Therefore, adhesive tapes used in closed spaces such as automobiles, houses, electronic devices, etc. are strongly required to have low odor and a low total amount of volatile gases that are environmentally hazardous substances. Yes.

In contrast, in Japan, the Ministry of Health and Welfare and the Ministry of Labor have issued guidelines for reducing the total amount of volatile organic compounds as well as reducing individual indoor volatile organic compounds as a countermeasure against sick houses in the residential field. Yes. The German Automobile Manufacturers Association (VDA) defines a method for evaluating the odor of a member used inside a vehicle by VDA270, and DVA277 and VDA278 are defined as a method for evaluating volatile components. Further, the German Industrial Association has established German Industrial Standard No. 75201 in order to determine the behavior of cloudiness due to volatile components generated from members. Thus, not only the reduction of specific volatile substances but also the reduction of various volatile substances is required in each field.

As a cause of volatile gas generated from a general adhesive tape, there are a residual solvent, a residual monomer, a residual polymerization initiator, a tackifier used for improving adhesive properties, and the like. Similarly, the cause of odor is volatile gas.
Patent Document 1 discloses a method of obtaining a pressure-sensitive adhesive with little residual monomer by polymerizing a monomer having a large molecular weight and a low saturated vapor pressure. Patent Document 2 discloses an adhesive using an acrylic polymer obtained by polymerizing a specific acrylic monomer in order to reduce odor. On the other hand, in Patent Document 3, a specific amount of azo polymerization initiator is used to reduce a volatile component, and a specific reaction temperature is set and solution polymerization is performed, thereby volatilizing residual initiator and unreacted monomer. A method for producing a pressure-sensitive adhesive tape using a pressure-sensitive adhesive obtained by producing a high-purity acrylic polymer with few components at a high polymerization rate is disclosed. Patent Document 4 discloses an adhesive tape having a low gas release level obtained by block copolymerization. Further, Patent Document 5 discloses a method for producing a hot-melt adhesive tape as an anti-fogging adhesive tape.

However, even in the case of these adhesive tapes, when used in a closed space such as in a house, vehicle, or electronic device, simply reducing a specific volatile component to a level at which humans do not perceive it as an odor. There was a problem that was not reached. Moreover, the high boiling point volatile component at the time of adding a tackifier is not considered, and about the general adhesive using a tackifier, the effect was not mentioned enough in the prior art.

Japanese Patent Laid-Open No. 6-122859 Japanese Patent Laid-Open No. 2-115291 JP 2002-69411 A Japanese Patent Laid-Open No. 2002-309210 Japanese Patent Laid-Open No. 11-315260

In view of the above situation, the present invention is an acrylic system that is preferably used for adhesion and fixing of a member used in a closed space where odor is a problem, such as in a vehicle or a house, or in an electronic device where volatile gas is a problem. It is an object of the present invention to provide an adhesive, an adhesive tape, and a vehicle air conditioner unit using the same.

The present invention 1 uses a polymerization initiator having a 10-hour half-temperature of 80 ° C. or lower, and maintains the reaction temperature higher than the 10-hour half-temperature as a polymerization condition. The content of the acrylic polymer polymerized under the condition satisfying the following formula (5) when the polymerization temperature at the end of polymerization at T _1/2 is T and the content of the component having a molecular weight of 600 or less is 13% by weight or less. It is an acrylic pressure-sensitive adhesive containing a tackifier and having a volatile component concentration A calculated by the following formula (1) of 500 ppm or less when heated at 90 ° C. for 30 minutes.

However, in formula (1), the volatile component amount X represents a toluene equivalent amount.

The present invention 2 uses a polymerization initiator having a 10-hour half-temperature of 80 ° C. or lower, and maintains the reaction temperature higher than the 10-hour half-temperature as a polymerization condition, and further reduces the 10-hour half-temperature of the polymerization initiator. The content of the acrylic polymer polymerized under the condition satisfying the following formula (5) when the polymerization temperature at the end of polymerization at T _1/2 is T and the content of the component having a molecular weight of 600 or less is 13% by weight or less. It is an acrylic pressure-sensitive adhesive containing a tackifier and having a volatile component concentration B calculated by the following formula (2) of 600 ppm or less when heated at 120 ° C. for 30 minutes.

However, in the formula (2), the volatile component amount Y represents an n-hexadecane conversion amount.

The present invention 3 is an adhesive tape having an adhesive layer comprising the acrylic adhesive of the present invention 1 or 2, and a volatile component calculated by the following formula (3) when heated at 90 ° C. for 30 minutes. The pressure-sensitive adhesive tape has a concentration C of 300 ppm or less.

However, in formula (3), the volatile component amount P represents a toluene equivalent amount.

The present invention 4 is an adhesive tape having an adhesive layer comprising the acrylic adhesive of the present invention 1 or 2, and a volatile component calculated by the following formula (4) when heated at 120 ° C. for 30 minutes. The pressure-sensitive adhesive tape has a concentration D of 400 ppm or less.

However, in the formula (4), the volatile component amount Q represents an n-hexadecane conversion amount.
The present invention is described in detail below.

Invention 1 is an acrylic pressure-sensitive adhesive having a volatile component concentration A calculated by the above formula (1) of 500 ppm or less when heated at 90 ° C. for 30 minutes.
If the volatile component concentration A obtained under these conditions is 500 ppm or less, the odor does not become a problem even when used in a closed space such as a vehicle or a house.

The volatile component amount X is, for example, a volatile component released when a weighed acrylic pressure-sensitive adhesive is heated at 90 ° C. for 30 minutes using a thermal desorption apparatus (for example, “ATD-400” manufactured by PerkinElmer Co., Ltd.). The amount can be measured by using a GC-MS apparatus (for example, “Automass II-15” manufactured by JEOL Ltd.). That is, for example, about 20 mg of an acrylic adhesive accurately weighed is placed in a sample tube (inner diameter: about 5 mm, length: about 10 cm), and helium gas is allowed to flow at 1.5 mL / min for 30 minutes while heating at 90 ° C. The volatile components obtained in this way are collected in a trap tube built in the thermal desorption device and concentrated, and then the trap tube is heated at 280 ° C. for 10 minutes and introduced into the GC-MS. For the GC-MS measurement, a nonpolar capillary column (manufactured by Agilent Technologies, HP-1; 0.32 mm × 60 m × 0.25 μm) was used, and the column temperature was maintained at 40 ° C. for 4 minutes, and then 5 minutes per minute. The temperature is raised to 100 ° C. at a rate of temperature rise of 100 ° C. After that, the temperature is raised to 320 ° C. at a rate of temperature rise of 10 ° C. per minute and then held at 320 ° C. for 3 minutes. The MS measurement range is 30 to 400 amu, the He flow rate is 1.5 ml / min, the ionization voltage is 70 eV, the ion source is 230 ° C., the interface is 250 ° C., and the transfer line is 225 ° C. The amount of volatile components can be calculated by weight-converting the obtained peak area based on an absolute calibration curve created with toluene.

In the acrylic pressure-sensitive adhesive of the present invention 1, the total amount of residual polymerization initiator detected by the above measurement conditions is 30 ppm or less, the total amount of residual acrylic monomer is 50 ppm or less, and the amount of volatile components having a retention time of 30 minutes or more. Is preferably 50 ppm or less. In such a case, the odor is further reduced.

The present invention 2 is an acrylic pressure-sensitive adhesive having a volatile component concentration B calculated by the above formula (2) of 600 ppm or less when heated at 120 ° C. for 30 minutes.
When the volatile component concentration B detected under these conditions is 600 ppm or less, there is no problem of odor, and since the total amount of volatile components with high boiling point is small, there is no problem of cloudiness. There is no problem even if it is used.

The volatile component amount Y can be measured, for example, by the same method as in the case of the acrylic pressure-sensitive adhesive of the first invention. However, in the GC-MS measurement, after maintaining the column temperature at 50 ° C. for 2 minutes, the temperature was increased to 160 ° C. at 25 ° C. per minute, and then increased to 300 ° C. at a temperature increase rate of 10 ° C. per minute. The obtained peak area is calculated in terms of weight based on an absolute calibration curve created with n-hexadecane.

The acrylic pressure-sensitive adhesive of the present invention contains an acrylic polymer as a main component. Although it does not specifically limit as said acrylic polymer, For example, the homopolymer of a (meth) acrylic acid ester monomer or the copolymer of a (meth) acrylic acid ester monomer and another vinyl monomer copolymerizable with this It is preferable that

As the (meth) acrylic acid ester monomer, an ester of a primary or secondary alcohol having 4 to 12 carbon atoms of an alkyl group and acrylic acid or methacrylic acid is preferably used.
The other vinyl monomer copolymerizable with the (meth) acrylic acid ester monomer is used to modify the acrylic polymer to increase the cohesive force. For example, its own glass transition point (Tg) Those that increase the Tg of the polymer that is obtained at a high level and those that contribute to the formation of a network between polymers by a crosslinking reaction between a functional group contained in the molecule and an external crosslinking agent are used.

Examples of the vinyl monomer for increasing the Tg of the resulting polymer include styrene, acrylonitrile, methyl methacrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and N-vinyl. Examples include pyrrolidone and the like. Examples of the vinyl monomer that contributes to the formation of a network between polymers by a cross-linking reaction between a functional group contained in the molecule and an external cross-linking agent include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, maleic anhydride. Examples thereof include carboxyl group-containing monomers such as acids; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and n-methylolacrylamide; and epoxy group-containing monomers such as glycidyl acrylate and allyl glycidyl ether.

When the acrylic polymer is a copolymer of a (meth) acrylic acid ester monomer and another vinyl monomer copolymerizable therewith, the content of the (meth) acrylic acid ester monomer is It is preferable to occupy 70% by weight or more. Moreover, when the Tg of the polymer from which the vinyl monomer is obtained is increased, the content of such a vinyl monomer is preferably 30% by weight or less. Further, when the vinyl monomer contributes to the network formation between the polymers by the crosslinking reaction between the functional group contained in the molecule and the external crosslinking agent, the content of such a vinyl monomer is that of the functional machine-containing monomer. The amount is preferably 0.1 to 10% by weight, more preferably 0.05 to 5% by weight.

The acrylic polymer can be obtained by a method of polymerizing the (meth) acrylic acid ester monomer or by copolymerizing a mixture of the (meth) acrylic acid ester monomer and a vinyl monomer copolymerizable therewith. It does not specifically limit as a polymerization method, For example, well-known polymerization methods, such as solution polymerization (boiling point polymerization, polymerization below boiling point), emulsion polymerization, suspension polymerization, block polymerization, and living polymerization, can be used. Among these, solution polymerization that does not use a surfactant or a dispersant is preferable.

It does not specifically limit as a polymerization initiator used when superposing | polymerizing the said acrylic polymer, For example, a peroxide polymerization initiator, an azo polymerization initiator, etc. are mentioned. As the polymerization initiator, those having a 10-hour half-life of 80 ° C. or less are preferred so that the polymerization initiator and its residue do not remain in the resulting acrylic polymer. These polymerization initiators may be used alone or in combination of two or more.

The peroxide-based polymerization initiator is not particularly limited. For example, peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide (lauroyl peroxide, benzoyl peroxide, 3, Organic peroxides such as 5,5-trimethylhexanoyl peroxide) and peroxyesters. Of these, peroxyesters having an acid residue of 8 or more peroxyester and an alcohol residue of 6 or less are preferred in terms of reducing the odor of the resulting acrylic polymer. Examples of such peroxyesters include t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethyl. Examples include hexanoate and t-butyl peroxylaurate.

In addition, diacyl peroxide, which is aliphatic having an acyl group having 8 or more carbon atoms, is also preferable from the viewpoint of reducing the odor of the resulting acrylic polymer. Examples of such a diacyl peroxide include lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, stearoyl peroxide, and the like.

The azo polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile), and azo compounds such as dimethyl 2,2′-azobisisobutyrate.

When polymerizing the above acrylic polymer, in particular, select a polymerization initiator having a 10-hour half-life temperature of 80 ° C. or less so that the polymerization initiator and its residue do not remain as volatile components in the reaction solution. In addition, it is preferable to carry out the reaction for as long as possible while maintaining the reaction temperature higher than the half-hour temperature for 10 hours as the polymerization conditions. Further, in order to reduce the residual polymerization initiator after the polymerization and allow the reaction to proceed rapidly and completely, the polymerization temperature T at the end of the polymerization is set within the range of the condition of the following formula (5), and this polymerization temperature is increased. It is preferable to keep the time.

As the acrylic polymer, the less unreacted monomer, unreacted polymerization initiator or other impurities remaining in the reaction liquid after polymerization, the more preferable, and the unreacted monomer at the time of polymerization or after completion of polymerization, if necessary. It is preferable to perform an operation for removing unreacted polymerization initiator and other impurities.

Specific means for reducing the residual monomer in the polymerization stage include, for example, a method of separating and removing the residual monomer in the refluxing solvent at the end of the polymerization; it is easily volatilized and removed by reacting with the acrylic monomer and the modified vinyl monomer. A method of adding a low-boiling scavenger monomer at the end of the polymerization can be mentioned.

As a method for removing the residual monomer from the polymerization system, for example, a method of replacing the reflux solution of the polymerization solvent with a fresh solvent; when the polymerization rate becomes 95% or more, preferably 98% or more, vinyl acetate, A method of adding a scavenger monomer having a relatively low boiling point such as vinyl butyl ether, methyl acrylate and styrene and removing the scavenger together with the scavenger; at the end of polymerization, a poor solvent for the acrylic polymer such as methanol, ethanol, n-hexane, Examples thereof include a method of washing an acrylic polymer using a low boiling point solvent such as n-heptane. These methods may be used independently and may use 2 or more types together.

The acrylic pressure-sensitive adhesive of the present invention may contain a tackifier for the purpose of improving pressure-sensitive adhesive properties. In this case, the tackifier preferably has a content of a component having a molecular weight of 600 or less of 13% by weight or less. By using such a tackifier, it is possible to obtain an acrylic pressure-sensitive adhesive that suppresses the volatile components generated from the tackifier without impairing the physical properties of the tack, improves the physical properties of the tack, and lowers the odor. Moreover, the n-hexadecane conversion amount of the volatile component released when the obtained acrylic pressure-sensitive adhesive is heated at 120 ° C. for 30 minutes can be suppressed to 600 ppm or less, and it is a high-boiling component that is difficult to remove by drying. The amount of volatile components for 30 minutes or more can be reduced to 50 ppm or less. In addition, the molecular weight of the said tackifier and its content can be measured by GPC, and can be calculated by a polystyrene conversion value and an area ratio.

Examples of the tackifier include rosin resins, rosin-modified phenol resins, disproportionated rosin ester resins, polymerized rosin esters, hydrogenated rosin resins, hydrogenated rosin ester resins, terpene phenol resins, coumarone indene resins. , Alkylphenol resins, petroleum resins and the like. Of these, rosin resins, polymerized rosin resins, alicyclic saturated hydrocarbon resins located in petroleum resins and the like are preferable because they can remove low molecular weight components.

Examples of the method for removing a component having a molecular weight of 600 or less from the tackifier include a method of heating and melting the tackifier above the softening point, and a method of blowing water vapor. When the tackifier is heated and melted, it is preferably heated in an inert gas such as nitrogen or helium in order to prevent an oxidation reaction with oxygen in the air. The heating time is preferably about 1 to 5 hours in order to avoid decomposition of the tackifier by heating. When water vapor is blown, when the pressure-reducing agent is decompressed to about 1 to 50 kPa after heating and melting, and then water vapor is blown, reduction of volatile components and reduction of odor are achieved. The time for blowing water vapor is preferably about 1 to 5 hours. If it is less than 1 hour, the effect of reducing large volatile gases and the accompanying odor is small, and the treatment effect does not change much even if treated for 5 hours or more.

Although it does not specifically limit as content of the said tackifier, It is preferable that it is 0.1 to 35 weight% with respect to an acrylic polymer.

The acrylic pressure-sensitive adhesive of the present invention may contain a crosslinking agent. By containing a crosslinking agent, it reacts with the functional group introduced into the acrylic polymer or the tackifier, and a crosslinked structure between the polymers or between the polymer and the tackifier is formed to increase the cohesive force. It does not specifically limit as said crosslinking agent, For example, an isocyanate type crosslinking agent, an aziridine type crosslinking agent, an epoxy-type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned.

The acrylic pressure-sensitive adhesive of the present invention may contain additives such as a plasticizer, an emulsifier, a softener, a filler, a pigment, and a dye as necessary. Similarly, it is preferable that volatile components are removed as much as possible.

The acrylic adhesive of the present invention is suitable as an adhesive layer for an adhesive tape. The pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive of the present invention is a member used in a closed space where odor is a problem, such as in a vehicle or a house, or an electronic device where volatile gas is a problem. It can be preferably used for adhesive fixation.
The present invention 3 is an adhesive tape having an adhesive layer comprising the acrylic adhesive of the present invention 1 or the present invention 2, and is a volatile component calculated by the above formula (3) when heated at 90 ° C. for 30 minutes. The pressure-sensitive adhesive tape has a concentration C of 300 ppm or less.

The present invention 4 is an adhesive tape having an adhesive layer comprising the acrylic adhesive of the present invention 1 or 2, and a volatile component calculated by the above formula (4) when heated at 120 ° C. for 30 minutes. It is a pressure-sensitive adhesive tape having a concentration D of 400 ppm or less.

The volatile component amount P or the volatile component amount Q can be measured, for example, by the same method as in the case of the acrylic pressure-sensitive adhesive of the present invention 1 or the present invention 2.

The pressure-sensitive adhesive tape of the present invention may be composed only of the pressure-sensitive adhesive layer made of the acrylic pressure-sensitive adhesive of the present invention, or may be one in which the pressure-sensitive adhesive layer is laminated on one side or both sides of the substrate. .
It does not specifically limit as said base material, For example, the sheet-like molded object which consists of paper, a nonwoven fabric, polyester, polyolefin, a polyurethane, a polychloroprene, a vinyl chloride resin, an acrylic resin etc. is mentioned. Moreover, you may use the thing which performed foaming as said base material. In order to achieve low odor, these substrates are also preferably composed of a previously purified material or have volatile components removed.

It does not specifically limit as a manufacturing method of the adhesive tape of this invention, A conventionally well-known method can be used. For example, a method of directly forming an adhesive layer on a substrate; a method of once forming an adhesive layer on a release-processed process paper, and transferring the adhesive on the process paper to the substrate, and the like.

Examples of the method for forming the pressure-sensitive adhesive layer include a method in which the acrylic pressure-sensitive adhesive of the present invention is applied on a substrate or process paper with a predetermined thickness and then the solvent is dried. When drying the solvent, increase the drying temperature as much as possible within the range in which the base material and process paper do not foam, increase the residence time in the drying furnace, set the drying furnace at a negative pressure, and the amount of drying air The amount of volatile components remaining on the pressure-sensitive adhesive tape of the present invention can be further reduced by performing a method for increasing the value. These methods are appropriately selected and used, and may be used in combination. Also, when the adhesive tape of the present invention is cured and stored, by adjusting the curing temperature, reducing the curing atmosphere, etc., the volatile components can be reduced, and the amount of generated volatile components and their odor can be reduced.

By using the pressure-sensitive adhesive tape of the present invention, it is possible to obtain an adhesive structure that is less likely to generate volatile gas that affects electronic devices due to the pressure-sensitive adhesive tape, and also less likely to generate odor due to the pressure-sensitive adhesive tape. it can. Among them, it is suitable for automobile interior applications where odor is a problem in a narrow space, and in particular, the vehicle air conditioner unit using the adhesive tape of the present invention is compared with that using a conventional adhesive tape. Thus, the odor is remarkably reduced.
The vehicle air conditioner unit using the adhesive tape of the present invention 3 or the present invention 4 is also one aspect of the present invention.

According to the present invention, an acrylic pressure-sensitive adhesive preferably used for adhesion and fixing of a member used in a closed space where odor is a problem in a vehicle, a house, etc., or an electronic device where volatile gas is a problem, An adhesive tape and a vehicle air conditioner unit using the same can be provided.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Reference Example 1)
In a reactor equipped with a thermometer, stirrer, condenser, dropping funnel and nitrogen gas inlet, from 70 g of n-butyl acrylate, 27 g of 2-ethylhexyl acrylate, 3 g of acrylic acid and 0.5 g of 2-hydroxyethyl methacrylate The monomer mixture obtained was dissolved in 83 g of ethyl acetate, and at the reflux point, 4 mmol of lauroyl peroxide (10-hour half-life: 62 ° C.) as a polymerization initiator was appropriately added from the start of polymerization to 4 hours to polymerize the acrylic monomer. After 4 hours, 2 mmol of the polymerization initiator was further added appropriately for 4 to 6 hours to reduce the residual monomer, and then the reaction was carried out for 10 hours to further reduce the residual monomer and the residual initiator (polymerization end). The obtained solution was cooled to obtain an acrylic polymer solution.

To 100 g of the obtained acrylic polymer solution, 1.5 g of a functional isocyanate-based cross-linking agent (manufactured by Nippon Polyurethane Co., Ltd. (Coronate L (active ingredient 55%))) was uniformly mixed to obtain an acrylic pressure-sensitive adhesive.
The obtained acrylic pressure-sensitive adhesive was applied to one side of a separator made of a polyethylene terephthalate film having a thickness of 50 μm so that the thickness after drying was 60 μm, and the solvent was completely removed by drying at 120 ° C. for 5 minutes. Produced.

(Reference Example 2)
An acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were produced in the same manner as in Reference Example 1, except that t-hexylperoxy-2-ethylhexanoate (10-hour half-life: 70 ° C.) was used as the polymerization initiator. .

(Reference Example 3)
An acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were produced in the same manner as in Reference Example 1 except that t-butylperoxy-2-ethylhexanoate was used as the polymerization initiator.

(Reference Example 4)
After 10 hours of reaction, an acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were produced in the same manner as in Reference Example 3 except that 5 g of vinyl acetate monomer was added.

(Comparative Example 1)
An acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were produced in the same manner as in Reference Example 1 except that the polymerization initiator was benzoyl peroxide (10-hour half-life 74 ° C.).

(Example 5)
To 100 g of the acrylic polymer obtained by the same method as in Reference Example 4, 25 g of a tackifier having a molecular weight of 600 or less and a component amount of 9.4% by weight was added and stirred uniformly, An acrylic pressure-sensitive adhesive was obtained by adding 1.5 parts of an agent (made by Nippon Polyurethane Co., Ltd., trade name “Coronate L”, active ingredient 55%) and stirring again uniformly.
The obtained acrylic pressure-sensitive adhesive was applied to one side of a separator made of a polyethylene terephthalate film having a thickness of 50 μm so that the thickness after drying was 60 μm, and dried at 120 ° C. for 5 minutes to prepare an adhesive tape.

(Comparative Example 2)
An acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were produced in the same manner as in Example 5, except that 25 g of a tackifier having a molecular weight of 600 or less was 15.6% by weight.

(Reference Example 6)
As a polymerization initiator, 4 mmol of t-butylperoxy-2-ethylhexanoate (10-hour half-life 70 ° C.) was appropriately added during the period from the start of polymerization to 4 hours, and further 3,5,5-trimethylhexahexane after 4 hours. An acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were prepared in the same manner as in Reference Example 4 except that 2 mmol of noyl peroxide was appropriately added to reduce the residual monomer.

(Example 7)
An acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive tape were prepared in the same manner as in Example 5 except that the acrylic polymer prepared in Reference Example 6 was used.

About the acrylic adhesives and adhesive tapes produced in Examples 5 and 7, Reference Examples 1 to 4 and 6 and Comparative Examples 1 and 2, odor, cloudiness, volatile component concentration and physical properties were evaluated by the following methods.
The results are shown in Table 1.

(Evaluation of odor)
Evaluation was performed according to VDA270. For evaluation, 50 cm ² of adhesive tape was sealed in a 1 L glass bottle, and after aging for 24 hours in an atmosphere of 40 ° C., the odor was evaluated immediately by the following 6-point method. In sensory evaluation, three or more panelists evaluated the adhesive tape by the following five-point method, and determined the average value.
1: Not perceptible 2: Perceptible but not unpleasant 3: Clearly perceptible but not so uncomfortable 4: Uncomfortable 5: Very uncomfortable 6: Unbearable

(Evaluation of cloudiness)
About 20 g of adhesive tape was put in a glass bottle with an internal volume of 100 ml, covered with a glass plate, heated at 120 ° C. for 24 hours, and the change of the glass plate was evaluated visually. The evaluation criteria are as follows.
○: No change.
Δ: There is a slight amount of cloudiness.
X: There is cloudiness that can be clearly confirmed.

(Measurement of volatile component concentration)
Using a thermal desorption device (“ATD-400” manufactured by PerkinElmer), the amount of volatile components released when the weighed adhesive tape was heated at 90 ° C. for 30 minutes and when heated at 120 ° C. for 30 minutes, The amount of volatile components was measured by using a GC-MS apparatus (“Automass II-15” manufactured by JEOL Ltd.), and the concentration of volatile components was calculated by the above formula (3) or (4). Further, the concentration of the volatile component of the pressure-sensitive adhesive was determined in advance by determining the ratio of the weight of the base material PET in the pressure-sensitive adhesive tape, and subtracting the weight of the base material from the weight of the pressure-sensitive adhesive tape (pressure-sensitive adhesive weight = pressure-sensitive adhesive weight-base (Material PET weight) was calculated by the above formula (1) or (2). In addition, about the PET base material, it confirmed that there was no volatile component in the case of a measurement beforehand.
For GC-MS measurement, a nonpolar capillary column (“HP-1” manufactured by Agilent Technologies; 0.32 mm × 60 m × 0.25 μm) was used, and when heated at 90 ° C. for 30 minutes, the column temperature was 40 After maintaining at 4 ° C. for 4 minutes, the temperature was raised to 100 ° C. at a rate of 5 ° C. per minute, raised to 320 ° C. at a rate of 10 ° C. per minute, and held at 320 ° C. for 3 minutes. . In addition, when heated at 120 ° C. for 30 minutes, the column temperature is maintained at 50 ° C. for 2 minutes, then the temperature is raised to 160 ° C. at 25 ° C. per minute, and then up to 300 ° C. at a rate of 10 ° C. per minute. The temperature was raised and held for 20 minutes.

The MS measurement range was 30 to 400 amu, the He flow rate was 1.5 ml / min, the ionization voltage was 70 eV, the ion source was 230 ° C., the interface was 250 ° C., and the transfer line was 225 ° C. The amount of volatile components was calculated by weight-converting the obtained peak area based on an absolute calibration curve created with toluene or n-hexadecane.
In addition, by the same method, the residual polymerization initiator total amount after heating at 90 ° C. for 30 minutes, the total residual acrylic monomer amount, and the volatile component amount having a retention time of 30 minutes or more were also measured.

(Evaluation of physical properties)
The adhesive strength of the obtained adhesive tape was measured according to JIS Z0237.

According to the present invention, an acrylic pressure-sensitive adhesive preferably used for adhesion and fixing of a member used in a closed space where odor is a problem in a vehicle, a house, etc., or an electronic device where volatile gas is a problem, An adhesive tape and a vehicle air conditioner unit using the same can be provided.

Claims (1)

10 hours half-life temperature as the polymerization initiator Ri der 80 ° C. or less, the carbon number of the acid residue of the peroxy ester is 8 or more, using a peroxyester having 6 or less carbon atoms the alcohol residue, and polymerization conditions And a condition that satisfies the condition of the following formula (5) when the polymerization initiator has a 10-hour half-life temperature of t _1/2 and a polymerization temperature at the end of the polymerization is T: in polymerized to prepare an acrylic polymer, the resulting acrylic pressure-sensitive adhesive in which the content of the acrylic polymer to the molecular weight of 600 or less components are blended tackifier is 13% by weight to prepare an acrylic pressure-sensitive adhesive The acrylic pressure-sensitive adhesive is a 50 μm-thick polyethylene terephthalate film that has been confirmed in advance to have no volatile components, and has a thickness after drying of 60 μm. The pressure-sensitive adhesive tape obtained by applying the acrylic pressure-sensitive adhesive as described above and completely drying and removing the solvent at 120 ° C. for 5 minutes was measured for the amount of released volatile component Y when heated at 120 ° C. for 30 minutes, and The ratio of the weight of the polyethylene terephthalate film in the pressure-sensitive adhesive tape is obtained in advance, and is calculated by the following formula (2) using the pressure-sensitive adhesive weight Z before heating obtained by subtracting the weight of the polyethylene terephthalate film from the weight of the pressure-sensitive adhesive tape. Volatile component density | concentration B is 600 ppm or less, The manufacturing method of the acrylic adhesive characterized by the above-mentioned.

However, in the formula (2), the volatile component amount Y represents an n-hexadecane conversion amount.