KR100418315B1 - Pressure Sensitive Adhesive - Google Patents

Abstract

The present invention relates to pressure sensitive adhesive compositions. The composition is a mixture of about 5 to 95 weight percent acrylic pressure sensitive adhesive and about 5 to 95 weight percent thermoplastic elastomeric copolymer. The form of the composition comprises at least two distinct regions wherein the first region is substantially continuous and the second region is fibrilos to shestoose that is substantially parallel to the major surface of the adhesive composition in the first region. The present invention also provides a pressure-sensitive adhesive tape and a method for producing the adhesive composition and the tape.

Description

Pressure sensitive adhesive

The present invention relates to a pressure-sensitive adhesive composition, specifically formed of two or more polymer materials, wherein at least one of them is a pressure-sensitive adhesive composition, a method for producing a pressure-sensitive adhesive and a pressure-sensitive adhesive component It is about a product.

Pressure sensitive adhesive tapes have been used for a variety of marking, holding, protecting, sealing and masking for over half a century. The pressure sensitive adhesive tape includes a backing or substrate and a pressure sensitive adhesive. Pressure-sensitive adhesives are materials that adhere only with acupressure and have a strong, permanent tack. The pressure sensitive adhesive does not require activation other than acupressure, exhibits a strong holding force and should be able to be removed from the smooth surface without leaving residue.

In some early uses of adhesives in the medical field, the product called adhesive plaster was not a pressure sensitive adhesive. In fact, they are plasticized with wood resin derivatives and a crude mixture of tackifying natural rubber with terpentin, darkly colored with zinc oxide. These tape-like products contributed to their purpose of use, but with the advent of true pressure sensitive adhesives they were replaced.

In the medical field, pressure-sensitive adhesive tapes are used in the hospital and health fields for a wide variety of applications, but basically they perform one of two functions. They are used in a variety of applications for fixation purposes, to pull something in place to limit movement, or to keep something in place, such as wound dressings. In each of the above functions, it is important that the pressure-sensitive adhesive tape adheres to the skin and does not irritate the skin, and adheres well to the skin without causing skin damage upon removal.

Similarly, the initial electrical tape was a black friction tape that was not pressure sensitive and the adhesive was very soft and therefore cracked when unwound. As true pressure sensitive adhesives were developed, they too were replaced by pressure sensitive adhesives. In general, more recent electrical tapes have pressure sensitive adhesives applied to plasticized polyvinyl chloride backings or polyethylene or rubber film backings. Electrical tape is used to insulate, maintain, strengthen, and protect electrical lines. Other applications include the provision of varnish impregnation matrices, the identification of wires in electrical circuits and the protection of terminals during the manufacture of electrical circuit boards. Electrical tapes must be flexible and consistent, and it is important to meet nonflammable requirements.

For packaging purposes, there is a need for a variety of tapes that can be used to seal packages, protect labels, isolate packaging from moisture, fix loose or bundle bundles. The packaging tape is exposed to continuous shear and low angle peel forces. In general, when the adhesive strength of the adhesive is low, it breaks in the shear direction; When imparting strength to the adhesive to improve shear resistance, it becomes less sticky and tends to be poor in adhesion.

Pressure-sensitive adhesives require an excellent balance of viscosity and elasticity, requiring a balance of four properties: adhesion, adhesion, elasticity and elasticity. Generally, pressure sensitive adhesives include elastomers or thermoplastic elastomers in which the elastomer is originally tacky or imparted with tackiness by adding a tackifying resin. Coating them in a solvent or with an aqueous emulsion can reduce the viscosity of the material to a level that can be easily applied to the selected substrate.

The main class of pressure sensitive adhesives are tackified natural rubbers; Synthetic rubbers such as butyl rubber; And tackified linear, radial, star, branched and tapered block copolymers such as styrene-butadiene, styrene-ethylene / butylene and styrene-isoprene; Polyvinyl ethers; Acrylics, especially acrylics having long chain alkyl groups; Poly- α -olefins; And silicon.

In general, when additives are used to enhance the properties of the pressure sensitive adhesive, these additives need to be miscible with the pressure sensitive adhesive, or must have some common block or group to be able to form a homogeneous mixture at the molecular level. do. Modifications can be made to pressure sensitive adhesives to extend their applicability to new fields. Tackified thermoplastic elastomers are dissolved in acrylic monomers and then cured. In addition, where each component contains a common fragment to allow compatibility, tackified thermoplastic elastomers have been added to the acrylic pressure sensitive adhesive polymerized in a solvent. This is due to the general purpose of associating the high shear properties of elastomers with the high adhesion of acrylics. In addition, there has been a continuing need to improve properties and to better balance these properties.

Summary of the Invention

The present invention comprises a mixture of at least about 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive and about 5 to 95 weight percent of at least one thermoplastic elastomeric material, wherein the pressure sensitive adhesive composition comprises at least two distinct regions. Wherein the first region is substantially substantially continuous and the second region is substantially fibrous to schist in parallel to the major surface of the adhesive composition in the first region. The thermoplastic elastomeric material may optionally contain a tackifying resin or plasticizer which may be present as an adhesive.

In addition, the present invention

(1) melt mixing at least about 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive and about 5 to 95 weight percent of at least one thermoplastic elastomeric material;

(2) (a) the melt mixed material is formed under one or both of shear conditions or stretching conditions, or

   (b) forming and drawing the molten mixture such that the first region is substantially substantially continuous in shape and the second region is substantially fibrous to schist in parallel to the major surface of the adhesive in the first region; Forming a pressure sensitive adhesive composition comprising distinct areas; And

(3) It provides a method for producing a pressure-sensitive adhesive composition comprising the step of cooling the composition.

The invention also includes a substrate comprising a mixture of about 5 to 95 weight percent acrylic pressure sensitive adhesive and about 5 to 95 weight percent thermoplastic elastomeric material, the pressure sensitive adhesive composition comprising two or more distinct regions. A pressure sensitive adhesive tape is provided, wherein the first region is substantially substantially continuous and the second region is fibrous to schist that is substantially parallel to the major surface of the adhesive in the first region on the substrate surface.

The present invention also provides an electrically pressure sensitive adhesive tape comprising a pressure sensitive adhesive composition comprising a substrate and a mixture of about 5 to 95 weight percent acrylic pressure sensitive adhesive on the substrate and about 5 to 95 weight percent thermoplastic elastomeric material. Wherein the composition is in a form comprising two or more distinct regions, wherein the first region is substantially substantially continuous and the second region is substantially fibrous to schist in parallel to the major surface in the first region. The substrate is preferably a polyvinyl chloride film or a film consisting of a mixture of ethylenevinyl acetate and ethylene-propylene-diene rubber.

In addition, the present invention

(1) melt mixing of about 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive and about 5 to 95 weight percent of at least one thermoplastic elastomeric material;

(2) (a) forming the melt mixed material under one or both of shear conditions or stretching conditions;

(b) forming and drawing the molten mixture, wherein the first region is substantially substantially continuous and the second region is substantially fibrous to schist in the direction of adhesive formation within the first region. Forming an adhesive composition comprising a form, and extruding the composition onto the surface of the substrate to form a pressure sensitive adhesive tape; And

(3) providing a method for producing a pressure-sensitive adhesive tape, comprising cooling the adhesive.

In addition, the present invention

(1) melt mixing about 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive and about 5 to 95 weight percent of at least one thermoplastic elastomeric material;

(2) (a) forming the melt mixed material under one or both of shear conditions or stretching conditions;

   (b) forming and drawing the melt mixture to form a pressure sensitive adhesive composition;

  (c) an adhesive in the form of a film-forming polymer resin, wherein the first region is substantially substantially continuous, and the second region comprises at least two distinct regions that are substantially fibrous to schist in the direction of adhesive formation within the first region. Co-extrusion of the composition; And

(3) It provides a method for producing a pressure-sensitive adhesive tape comprising the step of cooling the composition and the polymer resin.

In addition, the present invention comprises a mixture of about 5 to 95 weight percent acrylic pressure sensitive adhesive and about 5 to 95 weight percent thermoplastic elastomeric material on a first side, wherein the first region is substantially substantially continuous and the second region is Retain a pressure-sensitive adhesive composition in the form of at least two distinct regions that are substantially fibrous to schist, parallel to the major surface of the adhesive in the first region, and may be the same or different than retaining on the first side on the second side. Provided is a double coated pressure sensitive adhesive tape comprising a substrate having a pressure sensitive adhesive.

In addition, the present invention

(1) melt mixing at least about 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive with about 5 to 95 weight percent of thermoplastic elastomeric material;

(2) (a) forming the melt-mixed material under one or both of shear or stretching conditions, or

(b) forming and drawing the molten mixture, wherein the first region is substantially substantially continuous in shape and the second region is substantially distinct from at least two fibrous to schist in the direction of adhesive formation within the first region. Forming a pressure-sensitive adhesive composition comprising a region, supplying the composition to the outside of a feed block having three or more layers, and feeding a film-forming polymer resin to the stop of the feed block to double coat the pressure-sensitive adhesive Forming a tape; And

(3) provides a method of making a double coated pressure sensitive adhesive tape comprising cooling the tape.

The invention also includes a substrate and a mixture of about 5 to 95 weight percent acrylic pressure sensitive adhesive and about 5 to 95 weight percent thermoplastic elastomeric material on the substrate, the first region being substantially substantially continuous and the second region Provides a pressure sensitive adhesive composition for skin adhesion comprising a pressure sensitive adhesive composition in a form comprising at least two distinct regions that are substantially fibrous to schist, parallel to the major surface of the adhesive in the first region. Suitable substrates or backings include occlusive, ie substantially impermeable backings, such as films, foam materials and laminates thereof, and non-occluded, ie, air permeable backings, such as perforated polymer films, fabrics, Nonwovens such as entangled or melt blown webs and thermally embossed nonwoven webs.

Increased peel adhesion compared to single acrylic pressure sensitive adhesives and solution mixed acrylic / thermoplastic elastomeric pressure sensitive adhesives has elastic properties when the continuous areas are pressure sensitive adhesives and fibrous to schist, i.e., discontinuous or simultaneous continuous areas retain elastic properties1 Observation can be made when the species is not pressure sensitive. Adjusted tack and peel adhesion properties can be observed when the continuous region is not a pressure sensitive adhesive. When each polymeric material is a pressure sensitive adhesive, the composition exhibits enhanced peel adhesion compared to similar photosensitive adhesive mixtures formed and coated from solvents.

Pressure-sensitive adhesive of the present invention is a medical tape; Box sealing tape; Electrical tape; And reversible tapes, removable tapes and sheet materials. By properly selecting the polymeric material, adhesives of various desirable end-use properties can be devised. When used as an adhesive for skin contact, the compositions of the present invention have enhanced initial adhesion compared to acrylic pressure sensitive adhesives or thermoplastic elastomeric materials. Aged adhesion to the skin can also be manipulated, for example, by controlling the relative amounts of the acrylic pressure sensitive adhesive and the thermoplastic elastomer component.

1 is a cross-sectional view of the adhesive layer of Example 5 taken at 1000 times magnification using a scanning electron microscope (SEM) along a film forming direction.

2 is a surface view of an adhesive layer of Comparative Example C6, taken at 10 times magnification using an optical microscope.

3 is a cross-sectional view of the adhesive layer of Example 7 taken 6000 times magnified using a transmission electron microscope (TEM) along the film formation direction.

4 is a cross-sectional view of the adhesive layer of Example 8 taken 6000 times magnification using a TEM along the film forming direction.

5 is a cross-sectional view of the adhesive layer of Example 9 taken 6000 times magnification using a TEM along the film forming direction.

6 is a cross-sectional view of the adhesive layer of Example 11 taken at 3000 times magnification using SEM along the film formation direction.

FIG. 7 is a cross-sectional view of the adhesive layer of Example 13 taken 2000 times enlarged using SEM along the film formation direction. FIG.

8 is a cross-sectional view of the adhesive layer of Example 13 taken 2000 times magnification with SEM along the transverse web direction.

FIG. 9 is a cross-sectional view of the adhesive layer of Example 18 taken 1000 times enlarged using SEM along the film formation direction. FIG.

10 is a sectional view of Example 18, taken 1000 times magnification using SEM along the transverse web direction. FIG.

FIG. 11 is a cross-sectional view of the adhesive layer of Example 22 taken 2000 times magnified using SEM along the film forming direction. FIG.

12 is a cross-sectional view of the adhesive layer of Example 22 taken 2000 times magnification with SEM along the transverse web direction.

FIG. 13 is a cross-sectional view of the adhesive layer of Example 40 taken 1000 times enlarged using SEM along the film forming direction. FIG.

FIG. 14 is a plot of the mechanical mechanical analysis of Examples 24-26.

Generally the glass transition temperature of the acrylic pressure sensitive adhesive is about -20 ° C or less, and C ₃ -C ₁₂ alkyl ester components such as isooctyl acrylate, 2-ethyl-hexyl acrylate and n-butyl acrylate 100 to 80% by weight and polar components such as acrylic acid, methacrylic acid, ethylene vinyl acetate, N-vinyl pyrrolidone and styrene macromers. The acrylic pressure sensitive adhesive preferably comprises 0-20 wt% acrylic acid and 100-80 wt% isooctyl acrylate. Acrylic pressure sensitive adhesives can be self-adhesive or tackled. Useful tackifying resins for acrylics include rosin esters such as FORAL 85 commercially available from Hercules Incorporated and aromatic resins such as PICCOTEX LC-55WK available from Hercules Incorporated. And aliphatic resins such as ESCOREZ 1310LC, available from Exxon Chemical Company.

The second component of the pressure sensitive adhesive composition of the present invention is a thermoplastic elastomer material mixed with an acrylic pressure sensitive adhesive. The thermoplastic elastomeric material contains at least two fragments having a glass transition temperature of at least 50 ° C., that is, hard fragments and soft fragments, one of which is an elastic material. The material forms a pressure-sensitive adhesive composition having two or more distinct areas by selecting one that is sufficiently incompatible with the pressure-sensitive adhesive and not reactive at the temperature of use. Of course, one or more second components may be combined with the pressure sensitive adhesive. The second component may or may not be a pressure sensitive adhesive.

Thermoplastic elastomer materials useful in the present invention are, for example, linear, radial, star polymers and tapered styrene-isoprene block copolymers, such as KRATON® D1107P and Enychem elastomers available from Shell Chemical Company. EUROPRENE® SOL TE9110 sold by S Americas Incorporated; Linear styrene- (ethylene-butylene) block copolymers such as Kraton G1657 available from Shell Chemical Company, styrene-isoprene-styrene block copolymers such as Kraton D1119P commercially available from Shell Chemical Company, linear, radial and star styrene Butadiene block copolymers such as KRATON D1118X sold by Shell Chemical Company, Europren SOL TE6205 available from Enchemem Elastomers Americas Incorporated, Hytrel® marketed by DuPont Company. Polyether esters such as G3548 and poly- α -olefin-based thermoplastic elastomer materials such as those represented by the general formula-(CH ₂ CHR) _x where R is an alkyl group containing 2 to 10 carbon atoms and ethylene sold by Dow Plastics Company Poly- α- based on metallocene catalysts such as ENGAGE® EG8200, which is a 1-octene copolymer Olefins are mentioned.

These thermoplastic elastomer materials further lower their melt viscosity by modifying them with tackifying resins or plasticizers, thereby forming the finest dispersions of the smallest phase dimensions, preferably less than about 20 microns, when mixed with acrylic pressure sensitive adhesives. It can be done easily. Tackifying resins or plasticizers that can be used with the thermoplastic elastomer material are preferably miscible at the molecular level. That is, the tackifier or plasticizer is preferably soluble in any polymer fragment or all polymer fragments of the thermoplastic elastomeric material. Generally, the tackifying resin may be present in an amount of about 5 to 300 parts by weight, more typically about 200 parts by weight or less based on 100 parts by weight of the thermoplastic elastomeric material.

The acrylic pressure sensitive adhesive and the thermoplastic elastomeric material are mixed and coated using melt extrusion techniques. Mixing is performed by any method that achieves a substantially homogeneous distribution of the acrylic pressure sensitive adhesive and the thermoplastic elastomeric material. Mixtures of acrylic pressure sensitive adhesives and thermoplastic elastomeric materials are prepared by melt mixing components in a molten or softened state using a dispersible mixing, distributive mixing or apparatus that simultaneously performs dispersible and distributive mixing. Both batch mixing and continuous mixing can be used. Examples of batch mixing methods include Brabender (trade name) or Banbury (trade name) internal mixing and roll mixing. Examples of continuous mixing methods include single screw extrusion, double screw extrusion, disc extrusion, repeated single screw extrusion and pin barrel single screw extrusion. The continuous mixing method is a distributing member such as a joint transition member such as the C trademark (trademark), Fin mixing member and electrostatic mixing member, and Madock mixing member sold by Lapra Technology Limited, Shrewsbury, UK. Or a dispersible member, such as a Saxton mixing member.

After the mixing step, the softened or molten acrylic pressure sensitive adhesive and the thermoplastic elastomer material mixture are subjected to a shear or stretch deformation or both related treatment to form a substantially continuous phase region of the pressure sensitive adhesive, and the thermoplastic elastomer material is substantially fibrous to It is formed into a film having a form for forming a region that is schistous. When the tackifier is mixed with a thermoplastic elastomer material, which is also an adhesive material, the adhesive regions can be continuous or the regions can be simultaneous continuous. These treatments may be batchwise or continuous.

An example of a batch treatment involves placing a portion of the mixture between the target substrate to be coated and the release liner and pressing the composite structure in a heated flat press at a sufficient temperature and pressure to form a pressure sensitive coating of the desired thickness, The resulting film is cooled.

The continuous forming method is to draw the pressure-sensitive adhesive composition from the film die and then contact it with the moving plastic web or other suitable substrate. A related continuous method involves extruding the pressure sensitive adhesive composition and the coextruded backing material from a film die and then cooling to form a pressure sensitive adhesive tape. Another continuous forming method is to contact the pressure sensitive adhesive mixture directly with a rapidly moving plastic web or other suitable substrate. In this method, the pressure sensitive adhesive mixture may be applied to a moving web using a die having a flexible die lip, such as a reverse orifice coated die. After formation, the pressure-sensitive adhesive film can be solidified by quenching using direct methods such as cooling rolls or water baths and indirect methods such as air or gas impregnation.

It is preferable that the melt viscosity of each polymer component is similar. The ability to form finely dispersed forms is related to the viscosity ratio and concentration of the components. Shear viscosity is measured using capillary rheometry at shear rates approaching extrusion mixing conditions, ie 100 s ⁻¹ and 175 ° C. When a higher viscosity polymer material is present as the minor component, the viscosity ratio of the minor component to the major component is preferably less than about 20: 1, more preferably less than about 10: 1. When a lower viscosity polymeric material is present as a subcomponent, the viscosity ratio of the subcomponent to the main component is preferably about 1:10 or greater, more preferably about 1: 5 or greater. The melt viscosity of the individual polymer materials can be changed by adding plasticizers, tackifying resins or solvents or by changing the mixing temperature. If the use of a solvent is required, it is desirable to prevent foaming by removing the solvent prior to the coating step.

In addition, the at least one polymeric material may be easily stretched in the melt mixing and coating process, such as fipirose to schist, which is oriented in the web forming direction within substantially continuous or simultaneous continuous regions of other polymeric materials, for example. It is preferable to form a finely dispersed form having a molding sheet, a ribbon, fibers, a long piece, and the like. It is desirable that there is sufficient interfacial adhesion between the acrylic pressure sensitive adhesive component and the thermoplastic elastomer component to withstand shear and stretch deformations present during the molding step and to promote the formation of a continuous film.

If none of the polymeric materials can be easily stretched in melt mixing and coating, or if there is not enough interfacial adhesion, the pressure sensitive adhesive coating can be formed entirely discontinuously, resulting in the presence of granules in the tissue. By suitably selecting the mixing conditions, the accuracy of the melt viscosity, and the shear / stretch conditions during extrusion, the thickness of the fibrous to schist regions can be made sufficiently thin so that no delamination occurs from the areas that are substantially continuous or simultaneous. Although the thickness of the fibrous to schist region will vary depending on the particular mixture, for example polymer type, concentration, viscosity, etc., the thickness is preferably less than about 20 microns, more preferably less than about 10 microns, and less than about 1 micron. Most preferred.

The invention will be further described by the following examples which do not limit the scope of the invention. In the examples below, all parts, ratios and percentages are by weight unless otherwise indicated. The following test methods were used to evaluate and characterize the polymer materials and pressure sensitive adhesive compositions prepared in the Examples.

Shear viscosity

Shear viscosity was measured using a high pressure capillary flow meter (Leograph 2001, available from Gottfert Company). The flow meter was operated at 175 ° C. using a capillary die of 30 mm in length and 1 mm in diameter. At a shear rate of 100 s ⁻¹ , the apparent viscosity was calculated from the Poisley equation and converted to real viscosity using the Weisenberg-Ravinović calibration method.

180 ° peeling test

180 ° peel adhesion was tested on glass and / or smooth cast and biaxially oriented polypropylene films of a 1.25 cm wide and 15 cm long pressure sensitive adhesive tape sample. This sample adhered to the test surface by pushing the tape four times with a 2.1 kg (4.5 lb) roller. After aging at ambient temperature (˜22 ° C.) for about 1 hour, the tape was tested using a Model 3M90 slip / peel tester available from Instruments Inc. The test was performed at a peel rate of 30.5 cm / min (12 in / min) at 180 ° unless otherwise noted.

Shear strength test

Shear strength was measured on pressure sensitive adhesive tape samples at ambient temperature. A 12.7 mm x 12.7 mm (0.5 in x 0.5 in) piece of tape was pressed four times with a 2.1 kg (4.5 lb) roller to adhere to a stainless steel sheet. 1000 g weight was adhered to the sample. The time for decreasing weight was recorded.

Rotary ball adhesion test

The rotary ball adhesion test was performed according to the pressure sensitive tape association test PSTC-6. The test rolled a 7/16 inch steel ball on a slope (21 ° 30 ') column on a tape sample located at the bottom of the column on a flat surface and measured the distance the ball rolled on the tape before the steel ball stopped.

Electrical tape adhesion test

The pressure-sensitive adhesive electrical tape sample is a steel panel (adhesion to steel) at a rate of 30.5 cm / min according to the AS trademark standard method of testing pressure-sensitive adhesive coated tape for electrical insulation, namely AS trademark D1000-79, method A And web material (adhesion to backing).

Skin adhesion test

The skin adhesion test was performed by placing a tape sample 2.5 cm wide and 7.5 cm long on the back of a subject. Each tape reciprocated a 2 kg roller at a speed of about 30 cm / min. Adhesion to the skin was measured by the peel force required to remove the tape at a removal rate of 15 cm / min at 180 °. Adhesion was measured immediately after initial application (T ₀ ) and after 24 hours (T ₂₄ ) or 48 hours (T ₄₈ ). Generally preferred skin adhesion is about 30 to 100 g (1.2 to 3.8 N / dm) of T ₀ , about 150 to 300 g (5.8 to 11.5 N / dm) of T ₂₄ and about 150 to 300 g (5.8 to 11.5 N) / dm) T ₄₈ .

Skin adhesion lift test

When a 24 hour or 48 hour skin adhesion test was performed, a portion of the tape was lifted (peeled off) from the skin prior to removal of the tape sample and graded based on the following criteria:

0 no visible lift

1 Lift only on edge of tape

2 lifts in more than 1 to 25% of the test area

3 Lift at 25 to 50% of test area

4 Lift at 50 to 75% of test area

5 lifts in 75 to 100% of the test area

The result is the average of the results of nine tests. Preferred skin adhesives will generally exhibit an average rating of about 2.5 or less.

Skin adhesive residue test

When a 24-hour or 48-hour skin adhesion test was performed, the skin underneath the tape sample was visually observed to determine the amount of adhesive residue on the skin surface and graded based on the following criteria:

0 no visible residue

1 Residue only on the edge of the tape

2 1 to 25% of test sites have residue

3 25 to 50% of test sites have residue

4 50-75% of the test site has residue

5 Residue at 75-100% of test site

The result is the average of the results of nine tests. Preferred skin adhesives will generally exhibit an average rating of about 2.5 or less.

Examples 1-6 and Comparative Example C1

In Example 1, the acrylic pressure sensitive adhesive (95 wt% isooctyl acrylate / 5 wt% acrylic acid, water emulsion polymerized, shear viscosity 150 Pa-s) is disclosed in U.S. Patent RE 24,906 (Urich), which is incorporated herein by reference. ), And after drying, using a twin-screw extruder (LEISTRITZ® model LSM34GL, commercially available from Leastriz Incorporated), which fully engages and co-rotates with a diameter of 34 mm. Thermoplastic elastomer Kraton® D1107P (styrene-isoprene-styrene block copolymer, shear viscosity 1250, premixed with 1% by weight of Irganox® 1010 antioxidant sold by Ciba-Geigy Co., Ltd. Pa-s) and melt mixed. The thermoplastic elastomer block copolymer was introduced into the feed port of the extruder, and the acrylic pressure sensitive adhesive was introduced into 4 zones. The temperature was gradually increased from 38 ° C. to 177 ° C. (100 ° F. to 350 ° F.) from zone 1 to zone 4. The feed rate was adjusted such that the ratio of pressure sensitive adhesive to thermoplastic elastomer block copolymer was 75:25.

The double screw extruder is a 25.4 cm (10 in) wide film die (UTLTRAFLEX® 40 die, model 89) at a pressure of approximately 0.69 MPa (100 psi). The die was continuously discharged into a three-layer feed block (CLOEREN® Model 92-1033) stacked on -12939. The die was maintained at 177-191 ° C (350-375 ° F) with a die gap of 0.5 From 20 to 30 mils, the mixed adhesive composition is extruded through the two outer portions of the extruder without using the center of the feed block and is biaxially oriented polyethylene terephthalate 51 μm (2 mil) thick 6.4 kg / hour (14 lbs / hour) were fed between the film and the peel coated paper web, at 7.3 m / min (24 fpm) between cooling rolls maintained at 21 ° C. (70 ° F.). Supplied to form a pressure-sensitive adhesive tape. C. In Examples 2, 3 and 4, the thermoplastic elastomer block copolymer Kraton D117P (styrene-isoprene-styrene block copolymer, shear viscosity 690 Pa-s) premixed with 1% by weight of Irganox 1010 was acrylic. It was added to the pressure sensitive adhesive so that the ratio of acrylic adhesive to thermoplastic elastomer block copolymer was 75:25, 63:37 and 25:75. In Example 5, the thermoplastic elastomer block copolymer was Kraton D1118X (butadiene-styrene Block copolymer, shear viscosity 1160 Pa-s), which was added to the acrylic pressure-sensitive adhesive with a ratio of acrylic adhesive to thermoplastic elastomer block copolymer of 82:18 In Example 6, the thermoplastic elastomeric polymer was stereon 827. (Styrene-butadiene multi-block copolymer, shear viscosity 2040 Pa-s, commercially available from Firestone Synthetic Rubber and Latex Company) Acrylic pressure-sensitive adhesive was added to the acrylic adhesive agent for a thermoplastic elastomer block copolymer of the ratio of 82; was adjusted to 18. In Comparative Example C1, pressure sensitive adhesive tapes were made with only acrylic pressure sensitive adhesives without other polymers.

The viscosity ratio of the discontinuous component to the substantially continuous component and the thickness of the adhesive on each pressure sensitive adhesive tape sample were measured, and the 180 ° peel adhesion test on glass and 180 ° peel adhesion test for biaxially oriented polypropylene (BOPP) were performed. Was performed. The results are shown in Tables 1a and 1b below. Moreover, the form of the adhesive composition of Examples 1-6 was also determined.

As can be seen from the data in Table 1 above, the addition of the thermoplastic elastomer block copolymer to the acrylic pressure sensitive adhesive was applied to both the glass and biaxially oriented polypropylenes of Examples 1, 2, 3, 5 and 6. The peel adhesion of the was increased. Example 4 demonstrates that when an excess of thermoplastic elastomer block copolymer is used, the adhesive properties of the adhesive composition can be controlled. The peel value of this adhesive suggests that the adhesive is suitable as a locator adhesive. In this example, the acrylic adhesive forms a substantially continuous region, the shape of which is similar to schist or ribbon. In Example 4, the thermoplastic elastomer block copolymer formed a substantially continuous region, the form of which was schist. The photomicrograph of the osmium stained adhesive layer of Example 5 taken with the scanning electron microscope (SEM) is shown in FIG. The darker part in the picture is acrylic adhesive.

Examples 7-9 and Comparative Examples C2-C6

In Examples 7 to 9, the pressure-sensitive adhesive tape was prepared in the same manner as in Example 1, except that the thermoplastic elastomeric pressure-sensitive adhesive was commercially available from the thermoplastic elastomer (50 parts by weight of Kraton D1107P) and the tackifier resin (Gooder Tire & Rubber Company). 50 parts by weight of a wingtack plus (WINGTACK PLUS®) and an antioxidant (irganox 1010 1 part by weight) were replaced with a thermoplastic elastomeric pressure-sensitive adhesive. The shear viscosity of the adhesive was 35 Pa-s at 191 ° C. (375 ° F.). The ratios of acrylic pressure sensitive adhesive to thermoplastic elastomeric pressure sensitive adhesives were 70:30, 50:50 and 25:75, respectively, acrylic adhesive was added to the extruder at the feed port and thermoplastic elastomeric adhesive was added in four zones. The pressure sensitive adhesive tape of Comparative Example C2 was made of only acrylic pressure sensitive adhesive without using other polymers. The pressure-sensitive adhesive tape of Comparative Example C3 was prepared using only the thermoplastic elastomer block copolymer Kraton D1107P premixed with an antioxidant, tackifying resin Witta Plus and a weight ratio of 50/50.

The thickness of each adhesive was measured and a 180 ° peel adhesion test on glass and a 180 ° peel adhesion test on biaxially oriented polypropylene (BOPP) was performed. The results are shown in Table 2 below.

In Comparative Examples C4, C5 and C6, the acrylic pressure-sensitive adhesives and pressure-sensitive adhesives prepared using the block copolymer Kraton D1107P and the tackifying resin wingtack plus used in Examples 6 to 8 are acrylic adhesive to block copolymer / The ratios of tackifying resin adhesives were 70:30, 50:50 and 25:75, respectively, and dissolved in tetrahydrofuran while allowing the solution to contain 20% by weight adhesive and 80% by weight solvent. The solution was coated onto a biaxially oriented polyethylene terephthalate film having a thickness of 76 μm (3 mil) and dried at room temperature to obtain a film having a thickness of 38 μm. The pressure sensitive adhesive tape thus prepared was tested for 180 ° peel adhesion to glass. The results are shown in Table 3 below.

Example Thickness (㎛) 180 ° peeling strength (N / dm)  Glass BOPP C2 48 51 26 7 43 64 39 8 48 81 43 9 64 75 49 C3 56 95 65

As can be seen from the data in Table 2, the addition of thermoplastic elastomeric pressure sensitive adhesives to acrylic pressure sensitive adhesives increased 180 ° peel adhesion to glass and biaxially oriented polypropylene. In the form of these adhesive compositions, each of Examples 7-9 was in fact a schist, ie, layered form. In Example 7, the acrylic adhesive formed a substantially continuous region while the thermoplastic elastomeric adhesive was discontinuous. In Example 8, the regions were substantially simultaneous continuity. In Example 9, the thermoplastic elastomeric adhesive was substantially continuous, but the acrylic adhesive was discontinuous.

As can be seen from the data in Tables 2 and 3 above, the extrusion melt mixed adhesives of the present invention exhibited significantly better performance than the same adhesive compositions prepared by solvent coating. In the form of these solution coated adhesives, each adhesive has a discontinuous sphere of the acrylate adhesive in Comparative Examples C4 or C5 or a discontinuous sphere of the thermoplastic elastomeric adhesives of Comparative Examples C4 and C5 and a discontinuous sphere of the acrylate adhesive of Comparative Examples C6 The continuity region of the thermoplastic elastomeric adhesive of Comparative Example C6 was retained.

Examples 10 and 11 and Comparative Example C7

In Examples 10 and 11, double coated pressure sensitive adhesive tapes were prepared using the same melt mixing and extrusion process as in Example 1, wherein the weight ratio of acrylic pressure sensitive adhesive to thermoplastic elastomeric polymer was 85:15 and 70:30, respectively. And the polypropylene melt was fed to the stop of the chlorine feed block. The melt is coextruded to provide a double coated pressure sensitive adhesive tape having a polypropylene core of about 76 to 127 μm (3 to 5 mil) thick with an adhesive coating of 25 and 38 μm (1.0 and 1.5 mil) thick. Was prepared. In Comparative Example C7, the double coated pressure sensitive adhesive tape was prepared in the same manner as in Examples 10 and 11, but no thermoplastic elastomer was used. Each double coated pressure sensitive adhesive tape was tested for 180 ° peel adhesion to the glass. The test results for Examples 10, 11 and Comparative Example C7 were 678 N / dm (1730 g / in), 74 N / dm (1913 g / in) and 51 N / dm (1332 g / in), respectively. As can be seen, the addition of the thermoplastic elastomer to the acrylic coagulant markedly increased the 180 ° peel adhesion of the adhesive. In Examples 10 and 11, the form of the adhesive composition was schist, with the acrylic adhesive forming a substantially continuous region and the thermoplastic elastomer forming a ribbon-like discontinuous region. FIG. 6 is a cross-sectional view of the adhesive of Example 11 taken at 3000 times magnification in the film forming direction after dyeing with osmium tetraoxide. FIG.

Examples 12 and 13 and Comparative Example C8

In Examples 12 and 13, double coated pressure sensitive adhesive tapes were prepared in the same manner as Examples 10 and 11, replacing the suspension emulsion composition with the water emulsion polymerized acrylic pressure sensitive adhesive. Suspension polymerized acrylic pressure sensitive adhesives were prepared according to US Pat. No. 4,833,179 (Young et al.). The method of preparation is as follows: a 2 liter separation reactor equipped with a condenser, thermowell, nitrogen inlet, a motorized stainless steel stirrer and a heating mantle with a temperature regulator is charged with 750 g of tilde water and 2.5 g of zinc oxide. And 0.75 g of hydrophilic silica (CAB-O-SIL® EH-5, commercially available from Cabot Co., Ltd.), at 55 ° C. until the zinc oxide and silica are sufficiently dispersed while blowing nitrogen. Heated. At this point, add 480 g of isooctyl acrylate, 20 g of methacrylic acid, 2.5 g of initiator (VAZO® 64 available from Dupont Company) and 0.5 g of isooctyl thioglycolate chain transfer agent, Mixed together. The resulting solution with initiator and chain transfer agent was then added to the initial aqueous mixture maintained to stir vigorously (700 rpm) to give a good suspension. The reaction was continued for at least 6 hours with blowing nitrogen, during which the reaction was monitored to maintain the reaction temperature below 70 ° C. The resulting pressure sensitive adhesive was collected and mechanically pressed to have a solids content of at least 90%. In Comparative Example C8, the double coated pressure sensitive adhesive tape was prepared in the same manner as in Examples 12 and 13, but no thermoplastic elastomeric adhesive was used.

Each tape was subjected to a 180 ° peel adhesion test on the glass. The test results for Examples 12, 13 and Comparative Example C8 were 32 N / dm (830 g / in), 74 N / dm (1913 g / in) and 24 N / dm (615 g / in), respectively. This suggests that the addition of thermoplastic elastomers, in particular higher levels of addition, increases the peel strength of the acrylic adhesive.

In Examples 12 and 13, the acrylic adhesive regions were substantially continuous, and the thermoplastic elastomer formed a ribbon like layer, namely substantially schist phase. Fig. 7 is a cross-sectional view of the adhesive of Example 13 taken 2000 times in the film forming direction after dyeing with osmium tetraoxide. 8 is a cross-sectional view of the adhesive of Example 13 taken 2000 times in a direction perpendicular to the film forming direction after dyeing with osmium tetraoxide.

Examples 14-17 and Comparative Example C9

In Examples 14 and 15, the double coated pressure sensitive adhesive tape was prepared in the same manner as in Examples 12 and 13, but the acrylic adhesive was 465 g of isooctyl acrylate, 20 g of methacrylic acid, methacrylate-terminated polystyrene An acrylic pressure sensitive adhesive prepared by water suspension polymerization of Macromer (CHEMLINK® 4500, commercially available from Sartomer Company, 0.25 g of acrylicoxybenzophenone and 0.35 g of isooctyl thioglycolate) was used. In Comparative Example C9, the double coated pressure sensitive adhesive was prepared in the same manner as in Examples 14 and 15 except that Kraton D1107P, a thermoplastic elastomer block copolymer, was not used In Examples 16 and 17, the double coated pressure sensitive adhesive The tapes were prepared in the same manner as in Examples 14 and 15, respectively, but they were Kraton G1657 (styrene- (ethylene-butylene)-, a thermoplastic elastomer block copolymer. Styrene) is replaced by KRATON D1107P. A peel adhesion to glass of each of the pressure-sensitive adhesive tape was measured. The test results are presented in Table 4.

Example 180 ° peeling strength (N / dm) Shear strength (min) C9 32 27 14 55 37 15 66 29 16 17 43 17 22 38

As can be seen in Table 4 above, the addition of Kraton D1107P improved the 180 ° peel adhesion of the suspension polymerized acrylic adhesive, while the addition of Kraton G1657 improved the shear strength of the adhesive. The addition of Kraton G1657 did not improve the 180 ° peel adhesion of the adhesive because the elastic properties of the thermoplastic elastomers were insufficient in this particular mixture. In each of Examples 14-17, the acrylic adhesive regions were substantially continuous, with the thermoplastic elastomeric regions being schistous in Examples 14 and 15 and fibrous in Examples 16 and 17.

Examples 18 and 19

In Example 18, the acrylic pressure sensitive adhesive used in Example 1 was premixed with thermoplastic elastomer block polymer Kraton D1320X (multi-octagonal styrene / isoprene polymer, commercially available from Shell Chemical Company, 1 wt% Irganox 1010). ) And the ratio of acrylic adhesive to thermoplastic elastomer block copolymer was 80:20, with a twin-screw extruder (model ZSK available from Werner & Playderer Corp., Ramsey, NJ). 30), the thermoplastic elastomer block copolymer was supplied in one zone and the acrylic pressure sensitive adhesive was supplied in three zones. The mixture was extruded onto a polyethylene film using a contact die at a rate similar to that used in Example 1 to obtain a pressure sensitive adhesive tape. In Example 19, a pressure-sensitive adhesive tape was prepared in the same manner as in Example 24 except using polyolefin thermoplastic elastomer (Engage EG8200, shear viscosity 1030 Pa-s available from Dow Plastics Company) in place of the thermoplastic elastomer block copolymer. , The ratio of acrylic adhesive to thermoplastic elastomer was 90:10. The adhesive thickness and 180 ° peel adhesion to the glass were measured and the measurement results are presented in Table 5 below.

Example Adhesive Thickness (μm) Peel Adhesion (N / dm) 18 47 > 77 19 36 63

As can be seen in Table 5 above, the adhesive composition made from the acrylic pressure sensitive adhesive and the thermoplastic elastomeric polymer exhibited excellent 180 ° peeling adhesion. Examples 18 and 19 each had a substantially continuous acrylic adhesive region. In Examples 18 and 19, the thermoplastic elastomers formed schist and fibrous regions, respectively. Fig. 9 shows a cross-sectional view of the adhesive of Example 18 taken in the direction of film formation after dyeing with osmium tetraoxide. Fig. 10 shows a cross-sectional view of the adhesive of Example 18 taken in the transverse direction after dyed with osmium tetraoxide.

Examples 20-23 and Comparative Example C10

In Example 20, 75 parts by weight of the acrylic pressure-sensitive adhesive used in Example 1, 12.5 parts by weight of the thermoplastic elastomer block copolymer Kraton D1107P, 1 part by weight of the antioxidant Irganox 1010, and tackifying resin Ekorez 1310LC (Exon Chemical Company) 12.5 parts by weight of the mixture was melt mixed and extruded in the same manner as in Example 18 to form a pressure-sensitive adhesive tape. In Example 21, the light-sensitive adhesive tape was prepared in the same manner as in Example 20, but the fraction thereof was 50 parts by weight of the acrylic adhesive, 25 parts by weight of the thermoplastic elastomer block copolymer, 1 part by weight of the antioxidant, and 25 parts by weight of the tackifying resin. . In Example 22, the pressure-sensitive adhesive tape was prepared in the same manner as in Example 20, but the fraction thereof was 25 parts by weight of the acrylic adhesive, 37.5 parts by weight of the thermoplastic elastomer block copolymer, 1 part by weight of the antioxidant, and 37.5 parts by weight of the tackifying resin. It was. In Example 23, the pressure-sensitive adhesive was prepared in the same manner as in Example 20, but the thermoplastic elastomer block copolymer was Kraton D1112P (styrene isoprene-styrene block copolymer), and the fraction thereof was 50 parts by weight of the acrylic adhesive and the thermoplastic elastomer block. It was 25 weight part of copolymers, 1 weight part of antioxidant, and 25 weight part of tackifying resin. Each adhesive had a thickness of 25 μm (1 mil).

Comparative Example C10 was prepared in the same manner as in Example 20, but contained only an acrylic pressure sensitive adhesive. Pressure-sensitive adhesive tapes tested 180 ° peel adhesion to glass, shear strength and rotating ball tracks to fiberboard and polished steel. The test results are shown in Table 6 below.

Example Shear strength (min)  Rotating ball track (μm) Peel Adhesion (N / dm) FB SS C10 5 31 35 32 20 - 14 36 38 21 9 15 44 35 22 6 26 43 59 23 7 26 38 50

As can be seen in Table 6, the addition of the thermoplastic elastomer block copolymer and the tackifying resin improves the 180 ° peeling adhesion of the acrylic pressure-sensitive adhesive, the adhesive prepared using Kraton D1107P as the thermoplastic elastomer block copolymer A further improvement was seen in the composition, Example 22, with a significant increase in peel adhesion in the adhesive made using Kraton D1112 as the thermoplastic elastomer block copolymer. The adhesives of Examples 20-23 retained excellent rotating ball tracks of adhesives containing only acrylic pressure sensitive adhesives even when the amount of tackified thermoplastic elastomer was as high as 75% by weight. In Example 20, the acrylic adhesive formed a continuous region in which the thermoplastic elastomer / adhesive imparting resin formed a ribbon-like schistophase structure. In Example 21, the structure was in fact a schist with substantially simultaneous continuity between the acrylic adhesive region and the thermoplastic elastomer / adhesion imparting resin region. In Example 22, the thermoplastic elastomer / adhesive imparting resin formed a substantially continuous region where the acrylic adhesive was in the form of a ribbon-like schist. 11 is a cross-sectional view of the adhesive of Example 22 taken 2000 times in the film forming direction after dyed with osmium tetraoxide. 12 is a cross-sectional view of the adhesive of Example 22 taken in the transverse web direction after staining with osmium tetraoxide. In Example 23, the structure was virtually schist-free in that the acrylic adhesive region and the thermoplastic elastomer / adhesive imparting resin region were substantially co-continuous.

Examples 24-27 and Comparative Examples C11 and C12

In Examples 24 to 27, the acrylic pressure sensitive adhesive was prepared in the same manner as in Example 1. Core-exterior strands are made of a sheath made from a mixture of an acrylic adhesive core and a thermoplastic elastomer polymer (99 parts by weight of Kraton D1107P) and an antioxidant (1 part by weight of Irganox 1010 available from Ciba-Geigy Co., Ltd.). Retained. The ratios of acrylic adhesive, thermoplastic elastomer and antioxidant used in Examples 24 to 27 were 70: 30: 1, 75: 25: 1, 80: 20: 1 and 70: 30: 1, respectively. Strands were quenched in water, dried and fed into a Model ZSK 30 co-rotating twin screw extruder sold by Werner & Playderer Coporation. In Examples 24 to 27, the adhesive was a mixture of 80 parts by weight of ethylene-vinyl acetate and 20 parts by weight of ethylene-propylene-diene rubber at a coating weight of about 25 g / m ² (6 g / 155 cm ² ), and aluminum trihydrate Containing 20 parts by weight, 11 parts by weight of decabromodiphenyl oxide and 5 parts by weight of antimony trioxide, and containing polyvinyl chloride comprising a fire retardation system prepared as described in US Pat. No. 5,284,889, which is incorporated herein by reference. It coated on the film which is not. In Example 30, the adhesive was coated on a polyvinyl chloride film backing sold as 5A1Q801-1 in Nanya Plastics Coporation at a coating weight of 35 g / m ² (8.4 g / 155 cm ² ). In Comparative Example C11, the tape backing containing no polyvinyl chloride was used to prepare 75 g / m ² (18 g / 155 cm) of a mixture of 100 parts by weight of thermoplastic elastomer (Kraton D11077P) and 1 part by weight of antioxidant (Irganox 1010). The coating weight was ² ). In Comparative Example C12, the backing without polyvinyl chloride was coated with a coating weight of 47 g / m ² (11.4 g / 155 cm ² ) using only acrylic adhesive.

Peel adhesion of the adhesive to steel and backing at 20 ° C. and −18 ° C. was measured using an electrical tape adhesion test, and the result of the measurement was 29 g / m ² (7 g / 155 cm) using Equation 1 below. Normalized to coat weight of ² ):

Standardized adhesion = (measured adhesion x 0.45) / measured coating weight in grams

Wherein the coating weight is the adhesive weight per site of 155 cm ² (4 in x 6 in). The results are shown in Table 7 below.

As can be seen from the data in Table 7, the pressure sensitive adhesive tapes of the present invention of Examples 24 to 27 had better performance than using only one component alone for steel at 20 ° C. and backing at generally 20 ° C. Indicates. At −18 ° C., the pressure sensitive electrical tapes of Examples 24 to 27 exhibit significantly better performance than the tapes of Comparative Examples C11 and C12.

During coating of the adhesive material in Examples 24 to 26, an adhesive sample having a thickness of about 1 to 2 mm was collected from the die onto the polyester release liner. These samples were examined by mechanical mechanical analysis using a RHEOMETRIC® dynamics analyzer (commercially available from Leometric Scientific Incorporated). Fig. 14 shows the mechanical mechanical properties G ′ (ω) and tan ² δ obtained in the above measurement, where ---- represents Example 24, ... represents Example 25, and-represents Example 26. . Compliance values were calculated using J (t) = 1 / {G '(ω) x (1 + tan ² δ)}, where G' (ω) is equal to (tensile storage modulus) / 3 Shear storage modulus, J (t) is the shear creep compliance which measured the softness of the adhesive. The higher the J (t) value, the better the contact between the adhesive and the surface to which the adhesive is bonded. The results are shown in Table 8 below in cm ² / dyne.

Example 24 25 26 Tanδ at -20 ° C to -10 ° C to 23 ° C 0.790.390.30 0.820.440.33 1.130.560.32 G '(dyne / cm ² ) at -20 ° C -10 ° C at 23 ° C 5.0 x ^{10 6} 3.0 x ^{10 6} 7.8 x ^{10 5} 4.3 x ^{10 6} 2.0 x ^{10 6} 6.4 x 10 ⁵ 6.5x10 ⁶ 2.9x10 ⁶ 7.5x10 ⁵ J (t) (cm ² / dyne) at -20 ° C -10 ° C at 23 ° C 1.6x10 ^-7 3.1x10 ^-7 12.0x10 ^-7 1.8x10 ^-7 4.6x10 ^-7 15.0x10 ^-7 1.0x10 ^-7 3.0x10 ^-7 13.0x10 ^-7

As can be seen from Table 8 above, each of the pressure sensitive adhesive tates of Examples 24 to 26 had excellent compliance, and the tape of Example 25 was found to exhibit the best performance. Such compliance or softening means that the adhesive of the invention has good contact with the surface to which it bonds, and the peel adhesion of the adhesive is generally good.

Example 28 and Comparative Example C13

Pressure-sensitive adhesive tapes were prepared in the same manner as in Example 15 and Comparative Example C9. Ultraviolet irradiation was performed using UV processor model # QC120244ANIR, available from RPC Industries, Inc., using a medium mercury lamp for each tape sample. Irradiation was carried out in a fixed amount of 100 mJ / cm ² at 365 nm in an inert nitrogen atmosphere. The 180 ° peel adhesion and shear strength of the tape were measured. The measurement results are shown in Table 9 below, and the measurement results of Example 15 and Comparative Example C9 were also presented.

Example Peel Adhesion (N / dm) Shear Strength (min) (break mode) C9 31.5 27 (adhesion) 15 55.3 37 (adhesion) C13 37.1 21 (adhesiveness: pop-off) 28 71.7 216 (adhesion: pop-off)

Irradiation cure using ultraviolet light increases crosslinking, and as a result, the peel adhesion of tapes produced using the adhesive of the present invention is further increased. However, the most significant increase by irradiation was found to be shear strength. The irradiated tape of the present invention increased the shear strength by more than five times compared to the non-irradiated tape. Shear strength decreased after irradiation.

Examples 29-35 and Comparative Examples C14 and C15

The acrylic pressure sensitive adhesives described in Example 1 were mixed with Kraton D1107P in various ratios and coated by batch mixing and coating. In Examples 29 to 35, a total of 45 g of acrylic pressure sensitive adhesive and Kraton D1107P (99 parts premixed with 1 part Irganox 1010 antioxidant) were operated at 50 g Brabender (347 ° F.) Brabender® was charged into a sigma blade mixer. Kraton D1107P was added first, followed by acrylic pressure sensitive adhesive. The mixture was mixed at 50-75 rpm for 5 minutes. The relative amounts of acrylic pressure sensitive adhesive and Kraton D1107P to be mixed were 40.5 g and 4.5 g (Example 29), 33.75 g and 11.25 g (Example 30), 22.5 g and 22.5 g (Example 31), 18 g and 27 g (Example 32), 11.25 g and 33.75 g (Example 33), 6.75 g and 38.25 g (Example 34), 2.25 g and 42.75 g (Example 35). For each example, a pressure sensitive adhesive coated about 1-5 g of mixed material was prepared by placing between the coated release paper and a biaxially oriented polyethylene terephthalate film having a thickness of 50 to 75 microns. It was then placed between two aluminum plates (152 mm (6 in) x 152 mm (6 in)) in a hydraulic plate press. A pressure of 28 MPa (4000 psi) was applied at 138 ° C. (280 ° F.) for 0.6 seconds to produce a pressure sensitive adhesive coating having a thickness ranging from 76 μm (3 mils) to 102 μm (4 mils). The 180 ° peel adhesion to the glass of the tape was measured. The measurement results are shown in Table 10 below.

Example Acrylic Pressure Sensitive Adhesive (wt%) Kraton D1107P (wt%) 180 ° peeling strength (N / dm) C14 100 0 61 29 90 10 71 30 75 25 81 31 50 50 91 32 40 60 59 33 25 75 49 34 15 85 29 35 5 95 26 C15 0 100 0

The form of the adhesives of Examples 29 and 30 was a continuous acrylic pressure sensitive adhesive with a schist thermoplastic elastomer phase. The adhesives of Examples 31 and 32 had a co-continuous schist phase composed of acrylic pressure sensitive adhesive and thermoplastic elastomer. Examples 33-35 had a continuous, non-tacky thermoplastic elastomer phase with a discontinuous pressure sensitive adhesive schist phase. Because of the axial deformation of the flat press coating method, the phases are formed parallel to the plane of the coating. As can be seen in Table 10 above, the 180 ° peeling adhesion to the glass can be controlled by varying the ratio of the acrylic pressure sensitive adhesive and the thermoplastic elastomer. Behaviors in the range of reduced 180 ° peel adhesion and easy removal (Examples 32 to 35) have been demonstrated in enhanced 180 ° peel adhesion (Examples 29 to 31).

Examples 36 and 37

Acrylic pressure sensitive adhesive tapes were prepared in the same manner as in Example 29, but with different acrylic pressure sensitive adhesives, the ratio of acrylic pressure sensitive adhesive to thermoplastic elastomer was 80:20. In Example 36, the acrylic pressure sensitive adhesive used was a fully engaged, integrally screwed 18 mm Lacestreets station according to the general method described in US Pat. No. 4,619,979 (Corkner et al.), Incorporated herein by reference. Prepared by feeding a premix of isooctylacrylate: acrylic acid: isooctylthiocholiclate: Vazo (VAZO®) 64 (available from DuPont) in a rotary double screw extruder at a ratio of 90: 10: 0.05: 0.3. The extruder was not vented and the screw speed was maintained at 50 rpm. The temperatures in zones 1-8 were maintained at 72 ° C, 82 ° C, 92 ° C, 96 ° C, 100 ° C, 110 ° C, 115 ° C and 120 ° C, respectively. In Example 37, the acrylic pressure sensitive adhesive used was an n-butyl acrylic pressure sensitive adhesive prepared in a similar manner to the preparation of the 2-ethyl hexyl acrylic pressure sensitive adhesive of Example 36. Materials for preparing the adhesive include n-butyl acrylate, N, N-dimethylacrylamide: acrylic acid: 4-acryloxybenzophenone: isopropanol: and bazo (a ratio of 83: 15: 2: 0.2: 2: 0.3). Brand name) 64, the screw rotational speed of the extruder was 70 rpm, the temperature of zone 1 to zone 8 was maintained at 70 ℃, 81 ℃, 92 ℃, 96 ℃, 105 ℃, 110 ℃, 115 ℃ and 120 ℃, respectively. . In each example, the relative amounts of Kraton D1107P and Irganox 1010 premixed with the acrylic pressure sensitive adhesive were mixed with 100 parts thermoplastic elastomer to 2 parts antioxidant. Comparative Examples C16 and C17 were prepared in the same manner as in Examples 36 and 37, respectively, but did not use thermoplastic elastomers but only acrylic pressure-sensitive adhesives. The samples were tested for 180 ° peel adhesion to glass and the adhesive thickness and peel adhesion measurements are presented in Table 10a below.

Example Adhesive Thickness (μm) Peel Adhesion (N / dm) 36 100 78 C16 100 63 37 100 108 C17 100 92

As can be seen from the data of Table 10a, the adhesive composition made of the acrylic pressure-sensitive adhesive and the thermoplastic elastomer block copolymer showed 180 ° peel adhesion superior to the 180 ° peel adhesion of the comparative example containing no thermoplastic elastomer. The form of the adhesive composition was a continuous acrylic pressure sensitive adhesive phase with a schist thermoplastic elastomer phase.

Example 38

In Example 38, the pressure-sensitive adhesive tape was the acrylic pressure-sensitive adhesive used in Example 1 and the thermoplastic elastomer polymer Hytrel 5326 (polyetherester commercially available from DuPont Company, shear viscosity was 495 Pa-s, Irganox 1010 1 weight It was prepared in the same manner as in Example 1 using% premixed). The ratio of the acrylic pressure sensitive adhesive and the thermoplastic elastomeric polymer was 80:20. The thickness of the adhesive was 60 μm, and the 180 ° peel adhesion to the glass was 40 N / dm. The form of the adhesive was a continuous acrylic pressure sensitive adhesive phase with a schist thermoplastic elastomer phase.

Examples 39-42 and Comparative Examples C18 and C19

In Examples 39, 40 and 41, the water suspension polymerized acrylic pressure sensitive adhesives described in Examples 12 and 13 were model ZSK 30 co-rotating dual bearing barrels 30 mm in diameter and 37: 1 in length to diameter ratio. In a screw extruder, it was mixed with a thermoplastic elastomeric adhesive (prepared by mixing 50 parts of thermoplastic elastomer block copolymer Kraton D1107P, 1 part of antioxidant Irganox 1010 and 50 parts of tackifying resin Escorez 1310LC), which was used as an acrylic pressure-sensitive adhesive The ratios of the thermoplastic elastomeric adhesives were 75:25, 50:50 and 25:75, respectively. The thermoplastic elastomer block copolymer was supplied in 1 zone, the tackifying resin was introduced in 2 zones, and the acrylic pressure sensitive adhesive was added in 3 zones. The temperature was maintained between 149 and 165 ° C. In Example 42, the pressure sensitive adhesive tape was prepared using the water emulsion polymerized acrylic pressure sensitive adhesive described in Example 1 and the thermoplastic elastomer described in Example 29, with a ratio of 75:25. In Comparative Example C18, the pressure sensitive adhesive tape was made using only acrylic adhesive. In Comparative Example C19, the pressure sensitive adhesive tape was made using only tackified thermoplastic elastomeric adhesive. The adhesive film thickness of all samples was about 50 μm (2 mil) and was coated on a non-obstructive, ie breathable woven backing, which was a 180 × 48 plain weave acetate taffeta fabric, 75 denier fibers in the winding direction and 150 in the filling direction. Denier fibers, available from Milliken & Company, Spartanburg, Georgia, USA. The adhesive compositions of Examples 39 and 42 exhibit substantially continuous acrylic adhesive regions in which the thermoplastic elastomer / adhesive imparting resin forms schist ribbon-like regions. In the adhesive composition of Example 40, the acrylic adhesive and the thermoplastic elastomer / adhesive imparting resin formed a substantially simultaneous continuous schist region. In Example 41, the thermoplastic elastomer / adhesive imparting resin formed a substantially continuous region, while the acrylic adhesive formed a schist ribbon-like region. Fig. 15 shows the adhesive of Example 40 taken with the film forming direction after dyeing with osmium tetraoxide. Pressure sensitive adhesive tapes were tested for skin adhesion immediately after application (T ₀ ) and after 24 hours (T ₂₄ ), skin adhesion lift after 24 hours, and skin adhesion residues after 24 hours. The results are shown in Table 11 below.

As can be seen in Table 11 above, the pressure-sensitive adhesive tapes of Examples 39 to 42 exhibited enhanced peeling ability from the skin, and T ₀ : T ₂₄ adhesion was appropriate for acrylic adhesives and thickened or un thickened thermoplastic elastomers. Can be adjusted by mixing. In particular, the tapes of Example 40 exhibited 180% to 33% greater initial adhesion to the skin than tapes made with any pressure sensitive adhesives of Comparative Examples C18 and C19. In addition, all examples showed acceptable 24-hour aging adhesion to the skin.

Examples 43-45

In Example 43, the acrylic pressure sensitive adhesive used in Example 12 was a thermoplastic elastomer adhesive (100 parts of thermoplastic elastomer block copolymer Kraton D1107P, 1.5 parts of Irganox 1076, an antioxidant commercially available from Ciba-Geigy, USA, 1.5 parts of CYANOX® LTDP, an antioxidant sold by American Sanamide Cooprationshon, New Jersey, and a tackifying resin marketed by Goodyear Chemical Company of Akron, Ohio, USA 70 parts of wingtack plus) was melt mixed, and the ratio of acrylic adhesive to thermoplastic elastomeric adhesive was 65:35. The melt mixing was carried out using a screw pin barrel mixer with a diameter of 8.9 cm available from The French Oil Mill Machinery Company, Piqua, Ohio, USA, and the zone temperature was raised to 106-144 ° C., 1 part water per 100 parts of the composition was injected when the pressure sensitive adhesive composition left the pin barrel mixer. A gear pump attached to the outlet end of the pin barrel mixer by a heated pipe transfers the pressure sensitive adhesive composition to a wipe-film coated die maintained at 160 ° C. to produce the non-obstructive (breathable) weave used in Examples 39-42. The adhesive composition was coated on the backing at a rate of 1.8 kg / hour / 25 cm die width. The backing speed was adjusted to produce an adhesive film with an average thickness of about 50 μm (2 mils). In Example 44, the pressure-sensitive adhesive tape was prepared the same as in Example 42, but the thermoplastic elastomeric adhesive was a thermoplastic elastomer block copolymer (kraton D1119, styrene-isoprene-styrene block copolymer, shear viscosity 17 Pa-s, shell 50 parts commercially available from Chemical Company), 2 parts Irganox 1076 as an antioxidant and 48 parts of wingtack plus as a tackifying resin were prepared. In Example 45, the pressure-sensitive adhesive tape was prepared in the same manner as in Example 43, but the acrylic pressure-sensitive adhesive used in Example 1 was 50 parts of Kraton D1107P, a thermoplastic elastomer block copolymer, 1 part of Irganox 1010, an antioxidant, and It was melt mixed with a thermoplastic elastomeric adhesive prepared by mixing 50 parts of Escolarez 1310LC, a tackifying resin, and the ratio of acrylic adhesive to thermoplastic elastomeric adhesive was 25:75, and the pressure-sensitive adhesive composition was supplied at a speed of 15.1 kg / hour, Zone temperature was maintained at 124-131 ° C. The adhesive compositions of Examples 43 and 44 exhibited substantially continuous acrylic adhesive regions in which the thermoplastic elastomer / adhesive imparting resin forms schist ribbon-like regions. The adhesive composition of Example 45 exhibited substantially continuous thermoplastic elastomer / adhesive resin regions in which the acrylic adhesive formed the schist ribbon-like regions. The pressure sensitive adhesive tape was tested for skin adhesion immediately after application (T ₀ ) and after 48 hours (T ₄₈ ), skin adhesion lift after 48 hours, and skin adhesion residues after 48 hours. The results are shown in Table 12 below.

Example T ₀ (N / dm) T ₄₈ (N / dm) T ₂₄ lift T ₂₄ residue 43 4.9 12.0 1.9 1.6 44 4.6 10.8 1.9 1.7 45 2.1 5.4 0.7 0.3

As can be seen in Table 12 above, the pressure sensitive adhesive tapes of Examples 43-45 with non-occluded woven backing and different acrylic pressure sensitive adhesives and thermoplastic elastomeric adhesives exhibited acceptable peeling ability from the skin.

Examples 46-48

In Examples 46-48, pressure-sensitive adhesive tapes were prepared using various non-occluded backing, melt mixing, and coating methods using the same thermoplastic elastomeric / tack-adhesive resin adhesive used in Example 45. The acrylic adhesive was the same as used in Examples 12 and 13. In Example 46, the ratio of acrylic adhesive to thermoplastic elastomeric adhesive was 60:40 and the pressure sensitive adhesive composition was coated on the release liner and laminated to the nonwoven rayon fiber backing. The backing primarily passes 1.5-denier viscous rayon staple fibers, 2.5-5 cm in length, through a double cylinder card (commercially available from Spinbau GmbH, Bremen, Germany) with a fiber weight of 41-54 g / m. ^{A two-} person baffle baffle fiber web was formed. The baffle baffle fibrous web is simultaneously compressed into a tissue-like state, and the lower lip of the ribs is a water bath of fiber-bonded rubber acrylate sizing latex (RHOPLEX® B-15, available from Rohm and Haas Company). It was fed through a nip of a pair of horizontal squeeze rolls immersed in a suitable size, diluted with water to a size substantially the same as the weight of the fiber, and dried. In Example 47, the ratio of the acrylic adhesive to the thermoplastic elastomeric adhesive was 50:50, the pressure-sensitive adhesive composition was applied to the liner, and the melt blown microfibers were blown on the adhesive at a rate of 450 g / hour / cm to increase the thickness. A backing with 80 μm and a basis weight of 20 g / m ² was formed. The melt blown microfibers have a diameter of about 5 to 10 μm, and US Pat. No. 5,230,701 using PS 440-200 polyurethane commercially available from Morton International Inc., Seabrook, New Hampshire, USA. It prepared by the method similar to the method described in Example 1. In Example 48, the ratio of acrylic adhesive to thermoplastic elastomeric adhesive was 60:40, and the pressure sensitive adhesive composition was Sontara, registered as a entangled polyester nonwoven substrate having a basis weight of 44 g / m ² commercially available from DuPont. 8010 backing was applied to a thickness of 0.65 mm. In the adhesive compositions of Examples 46-48, the acrylic adhesive and the thermoplastic elastomer / adhesive imparting resin adhesive formed a substantially simultaneous continuous schist phase region. The pressure sensitive adhesive tape was tested for skin adhesion immediately after application (T ₀ ) and after 48 hours (T ₄₈ ), skin adhesion lift after 48 hours, and skin adhesion residues after 48 hours. The thickness and test results of each adhesive composition are shown in Table 13 below.

Example Thickness (㎛) T ₀ (N / dm) T ₄₈ (N / dm) T ₄₈ lift T ₄₈ residue 46 21 2.1 6.5 0.1 0.6 47 39 2.6 6.1 0.5 0.0 48 32 3.5 12.0 0.9 4.8

As can be seen in Table 13 above, the pressure sensitive adhesive tapes of Examples 46 to 48 with non-occluded woven backing and different acrylic pressure sensitive adhesives and thermoplastic elastomeric adhesives exhibited acceptable peeling ability from the skin.

Examples 49-52

In Examples 49-52, pressure sensitive adhesive tapes were prepared in the same manner as Examples 46-48, with various obstructive non-breathable backings used. In Example 49, the ratio of the acrylic adhesive to the thermoplastic elastomeric adhesive was 60:40, and the pressure sensitive adhesive composition was 117 μm thick prepared using ESCORENE® S-31209 available from Exxon Chemical Company. The polyethylene / vinyl acetate copolymer film was applied. The film was perforated at about 100 holes / cm ² . In Example 50, the ratio of acrylic adhesive to thermoplastic elastomeric adhesive was 60:40, and the pressure sensitive adhesive composition was applied to a 76 μm thick low density polyethylene film made using NA 964-085 resin commercially available from Quantum Chemical Company. . In Example 51, the ratio of the acrylic adhesive to the thermoplastic elastomeric adhesive was 50:50, and the pressure sensitive adhesive composition was 0.57 mm thick plasticized polyvinyl chloride foam (General Foam Co., Ltd., Karlstad, NJ). No. 9058 TA 022 Plestone, commercially available from Sean. In Example 52, the ratio of acrylic adhesive to thermoplastic elastomeric adhesive was 50:50, and the pressure sensitive adhesive composition was applied to Engage 8200 (Dow Plastics Company) extruded onto a 44 x 36 woven fabric (available from Burcot Mills). Commercially available polyolefin elastomers) on the polymer side of the white polymer / fabric laminate. The white backing was dry mixed with 1 part of 50:50 titanium dioxide and 3 parts of Enga 8200 in a low density polyethylene (marketed as PWC00001 in Hold Spectrum, Massachusetts, USA); Melt mixing, extruding and pelleting the strands in a 40 mm double screw extruder (commercially available from Berstov) at 200 ° C. to form colored pellets; Dry mixing the colored pellets and more uncolored Engagement 8200 in a ratio of 1:25; The mixture was melt mixed and placed on a Davis Standard Model N 9485 single screw extruder (6.4 cm in diameter, Connecticut, USA) at a rate of about 270 g / min at a temperature of 204 ° C. (400 ° F.). 66 μm (2.6 mil) thick film onto a fabric using a casting roll fixed at 93 ° C. (200 ° F.) and supplied at a supply port of Davis Standard Division of Cromphton & Knowles Coporation. Extruding to form a laminate; The laminate was prepared by passing through two parallel roll nips at a speed of about 11 m / min (about 35 fpm) at a pressure of 350 N / cm. In the adhesive compositions of Examples 49, 50, and 52, the acrylic adhesive and the thermoplastic elastomer / adhesion imparting resin adhesive formed substantially simultaneous continuous schist regions. In the adhesive composition of Example 51, the acrylic adhesive formed a substantially continuous region, and the thermoplastic elastomer / adhesive imparting resin formed a ribbon like schist region. The pressure sensitive adhesive tape was tested for skin adhesion immediately after application (T ₀ ) and after 48 hours (T ₄₈ ), skin adhesion lift after 48 hours, and skin adhesion residues after 48 hours. The thickness and test results of each adhesive composition are shown in Table 14 below.

Example Thickness (㎛) T ₀ (N / dm) T ₄₈ (N / dm) T ₄₈ lift T ₄₈ residue 49 29 2.4 1.8 1.3 0.6 50 39 2.1 1.5 0.9 0.6 51 39 5.6 7.6 0.3 1.8 52 50 1.5 3.7 1.1 0.3

As can be seen in Table 14 above, the pressure-sensitive adhesive tapes of Examples 49 to 52 with non-breathable backings that were occluded varied in peelability from the skin.

Example 53

The pressure sensitive adhesive tape was prepared using the method of Example 18 and the material of Example 52, but is an aluminum trihydrate commercially available from Salem Industries, Inc., Necrosis, Georgia, USA, per 100 parts of thermoplastic elastomeric adhesive. 10 parts of MICRAL® 1500 were premixed with a thermoplastic elastomeric adhesive. The thickness of the pressure sensitive adhesive was 50 μm. The acrylic adhesive and the thermoplastic elastomer / adhesion imparting resin adhesive formed a substantially simultaneous continuous schist phase region. The pressure sensitive adhesive tape was tested for skin adhesion immediately after application (T ₀ ) and after 48 hours (T ₄₈ ), skin adhesion lift after 48 hours, and skin adhesion residues after 48 hours. The skin adhesion was initially 1 N / dm, but after 48 hours it was 3.1 N / dm. After 48 hours, the skin lift lift was 1 and the skin adhesion residue was 0.

The present invention has been described above, and modifications of the present invention are apparent to those skilled in the art without departing from the scope of the present invention. In addition, the present invention is not limited to the details described herein for the purpose of illustration only.

Claims (5)

A pressure sensitive adhesive composition containing a mixture of about 5 to 95 weight percent of an acrylic pressure sensitive adhesive and about 5 to 95 weight percent of a thermoplastic elastomer copolymer, Wherein the composition comprises two or more distinct regions, wherein the first region is substantially substantially continuous, and the second region is substantially fibrous to schist, parallel to the major surface of the adhesive composition in the first region. Adhesive composition. (1) melt mixing 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive and 5 to 95 weight percent of at least one thermoplastic elastomeric material: (2) (a) the melt mixed material is formed under one or both of shear conditions or stretching conditions, or (b) forming and drawing the melt mixture such that the first region is substantially substantially continuous and the second region is substantially fibrous to schist in parallel to the major surface of the adhesive in the first region. Forming a pressure-sensitive adhesive composition comprising the above distinct areas: (3) cooling the composition Method for producing a pressure-sensitive adhesive composition comprising a. Description: and The pressure sensitive adhesive composition of claim 1 present on the substrate Pressure sensitive adhesive tape comprising a. materials; The pressure sensitive adhesive composition of claim 1 present on at least one side of the substrate; And A pressure sensitive adhesive present on the other side of the substrate Double coated pressure sensitive adhesive tape comprising a. (1) melt mixing 5 to 95 weight percent of at least one acrylic pressure sensitive adhesive and 5 to 95 weight percent of at least one thermoplastic elastomeric material; (2) (a) the melt mixed material is formed under one or both of shear conditions or stretching conditions, or (b) forming and drawing the melt mixture such that the first region is substantially substantially continuous and the second region is substantially fibrous to schist in the direction of film formation of the adhesive composition within the first region. Forming a pressure-sensitive adhesive composition comprising the above-described distinctive regions, and co-extruding the film-forming polymer resin and the pressure-sensitive adhesive composition; And (3) cooling the adhesive composition and the film forming polymer resin Method for producing a pressure-sensitive adhesive tape comprising a.

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