JP2000160117A - Double-sided adhesive sheet, its production, and control of its tackiness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a double-sided adhesive sheet with its tackiness easily controllable at low cost without impairing its designability, excellent in operability, to provide a method for producing such a double-sided adhesive sheet, and to provide a method for controlling the tackiness of such a double-sided adhesive sheet easily at low cost without impairing its designability. SOLUTION: This double-sided adhesive sheet is obtained by laminating each of both sides of a substrate 1 with a tack agent layer 2 and a nontacky layer 3 so as to expose part of the tack agent layer 2 over the whole surface, or by laminating one side of a substrate 1 with a tack agent layer 2 and a nontacky layer 3 so as to expose part of the tack agent layer 2 over the whole surface and laminating the other side with a tack agent layer 2 alone, or by laminating both sides of a tack agent layer 2 with nontacky layers 3 so as to expose part of the tack agent layer 2 over the whole surface. The 2nd objective method for producing such a double-sided adhesive sheet comprises laminating a nontacky layer 3 patterned on a release paper 4 with a tack agent layer 2 coated on a substrate 1. The 3rd objective method for controlling the 180 deg. tear-off tackiness of a double-sided adhesive sheet comprises altering the area ratio for the tack agent layer 2 and the nontacky layer 3 in contact with the adherend of either one of the above double-sided adhesive sheets.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a double-sided pressure-sensitive adhesive sheet,
The present invention relates to a manufacturing method thereof and a method of adjusting the adhesive strength.

[0002]

2. Description of the Related Art At present, the pressure-sensitive adhesive strength of a pressure-sensitive adhesive sheet is adjusted by considering the type and amount of a curing agent, mainly on the type of a pressure-sensitive adhesive, by making the pressure-sensitive adhesive finer, or by forming irregularities on the surface of the pressure-sensitive adhesive layer. It is adjusted by reducing the bonding area. However, production of various types of adhesives not only leads to an increase in manufacturing cost, but is often not enough to control adhesive strength widely. In addition, in the method of forming fine particles or making the surface of the pressure-sensitive adhesive uneven, the adhesive interface becomes uneven, and when the substrate supporting the pressure-sensitive adhesive layer is thin, the unevenness is reflected on the substrate and the In some cases.

[0003] Further, in the case where the adhesive strength between one side and the other side of the double-sided pressure-sensitive adhesive sheet is made different, similarly, it is necessary to prepare two types of adhesives having different adhesive strengths. Furthermore,
Since a transfer type sheet consisting of an adhesive layer alone without a base material, such as a core material or a support, is usually composed of one kind of adhesive, there is a difference in adhesive strength between one surface and the other surface. It was impossible to put on. For this reason, in the transfer type sheet, although the release force of the release paper that protects one side and the other side is different until the time of use, the difference in the release force is not enough, and only one side is released. Attempting to do so has many problems in operability, such as partial peeling from the surface of the other release paper.

[0004] The condition of a pressure-sensitive adhesive sheet that requires transparency is that the sheet itself is transparent, and how air bubbles mixed between the pressure-sensitive adhesive layer and the adherend during sticking work can be removed (air bubbles). (Removability). Conventionally, the pressure-sensitive adhesive sheet used in such applications reduces the pressure-sensitive adhesive strength of the pressure-sensitive adhesive to provide removability, or applies a surfactant or the like to the surface of the pressure-sensitive adhesive layer, and then applies the pressure-sensitive adhesive with water during construction. It is constructed by a method such as "wet paste" that is wet and pasted.
However, if the adhesive strength of the adhesive is reduced, the adhesive reliability is naturally lowered, and the method of applying water is a wet method using water at the time of construction, and requires a very complicated operation. In addition, as a method of preventing air bubbles from being mixed at the time of bonding, a material that reduces the adhesive area by providing minute unevenness on the surface of the adhesive layer that is in contact with the adherend and uses the concave portion as a passage for removing air bubbles is also used. is there. However, the point adheres to the adherend and the recess is difficult to contact with the adherend. Although there is no phenomenon such as "floating / swelling" due to bubbles, there is a part where air is interposed between the adhesive layer and the adherend layer. It was difficult to ensure complete transparency.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a double-sided PSA sheet which can be easily and inexpensively adjusted in adhesive strength without deteriorating design properties, has excellent operability, a method for producing the same, and without deteriorating design properties. It is an object of the present invention to provide a simple and inexpensive method for adjusting the adhesive strength of a double-sided adhesive sheet.

[0006]

Means for Solving the Problems The present inventors laminated the non-adhesive layer on the pressure-sensitive adhesive layer so that a part of the pressure-sensitive adhesive layer was exposed over the entire surface, thereby obtaining the adhesive strength of the double-sided pressure-sensitive adhesive sheet. The present invention has been found that a double-sided pressure-sensitive adhesive sheet having an excellent operability and excellent operability can be obtained. In addition, the present inventors have found that the adhesive force can be adjusted by changing the area ratio of the pressure-sensitive adhesive layer and the non-adhesive layer in contact with the adherend of the pressure-sensitive adhesive sheet, and the non-adhesive layer is patterned on release paper. It has been found that a pressure-sensitive adhesive sheet excellent in operability can be produced at low cost by laminating the pressure-sensitive adhesive layer with the pressure-sensitive adhesive layer after the above, and the present invention has been achieved.

That is, the present invention relates to a double-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer and a non-adhesive layer are laminated on both sides of a substrate such that a part of the pressure-sensitive adhesive layer is exposed over the entire surface.
Further, the present invention provides an adhesive layer and a non-adhesive layer on one surface of a substrate so that a part of the adhesive layer is exposed over the entire surface, and an adhesive layer on the other surface of the substrate. The present invention relates to a double-sided pressure-sensitive adhesive sheet obtained by laminating only the adhesive sheets. Further, the present invention relates to a double-sided pressure-sensitive adhesive sheet in which a non-adhesive layer is laminated on both surfaces of a pressure-sensitive adhesive layer such that a part of the pressure-sensitive adhesive layer is entirely exposed. The present invention also relates to the double-sided pressure-sensitive adhesive sheet, wherein the non-pressure-sensitive layer is a patterned resin layer.

In the present invention, the non-adhesive layer may have an area ratio between the adhesive layer and the non-adhesive layer of from 90:10 to 10:90, and may be a minimum repeating unit having an area of 5 mm × 5 mm or less,
The present invention relates to the double-sided pressure-sensitive adhesive sheet, which is a patterned resin layer. The present invention also relates to the double-sided pressure-sensitive adhesive sheet, wherein the 180-degree peeling pressure of the pressure-sensitive adhesive layer is adjusted by a non-pressure-sensitive layer. Further, the present invention, the non-adhesive layer,
When laminated on a 50μ thick polyethylene terephthalate film to form a 50μ dry film,
The present invention relates to the double-sided pressure-sensitive adhesive sheet described above, which is made of a material having a 180-degree peeling strength with respect to a test plate defined in JIS Z0237 of less than 10 gf / 25 mm. Also,
The present invention relates to the double-sided pressure-sensitive adhesive sheet, wherein the non-pressure-sensitive layer contains a resin having a glass transition point of 0 ° C. or higher.

The present invention also relates to the double-sided pressure-sensitive adhesive sheet, wherein the area ratio between the pressure-sensitive adhesive layer and the non-adhesive layer in contact with the adherend is different between one surface and the other surface. The present invention also relates to the double-sided pressure-sensitive adhesive sheet having a visible light transmittance of 75% or more. The present invention also relates to the double-sided pressure-sensitive adhesive sheet, which is used for temporary fixing and re-peeling. The present invention also relates to the double-sided pressure-sensitive adhesive sheet, which is used for blocking heat rays. The present invention also relates to the double-sided pressure-sensitive adhesive sheet, which is used for scattering prevention.
The present invention also relates to a method for producing the double-sided pressure-sensitive adhesive sheet, comprising laminating a non-adhesive layer patterned on release paper and a pressure-sensitive adhesive layer coated on a substrate. Also, the present invention
Patterning a non-adhesive layer on release paper, applying a pressure-sensitive adhesive layer thereon to make the non-adhesive layer and the pressure-sensitive adhesive layer substantially flush with the adherend on the double-sided pressure-sensitive adhesive sheet And a method for producing the same. Furthermore, the present invention relates to a method for adjusting the peeling strength by 180 degrees by changing the area ratio of the pressure-sensitive adhesive layer and the non-adhesive layer in contact with the adherend of any of the above double-sided pressure-sensitive adhesive sheets.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The transparency of the double-sided pressure-sensitive adhesive sheet of the present invention is 400 nm to 700 nm, which is a wavelength region of visible light.
It was evaluated by the light transmittance of nm. For the evaluation, a spectrophotometer (“U-best30” manufactured by JASCO Corporation) was used. At the time of measurement, nothing was inserted on the reference side, and the light transmittance in comparison with air was measured. Regarding the relationship between the light transmittance and the transparency, when the light transmittance is visually observed to be 70% or less,
It becomes turbid and the impression of transparency becomes faint. Therefore, in the present invention, 400 is used as a criterion for ensuring transparency.
The light transmittance is 7 in the entire wavelength region from 700 nm to 700 nm.
5% or more.

The base material of the double-sided pressure-sensitive adhesive sheet includes olefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate, cellophane, polyvinylidene chloride, polyvinylidene chloride copolymer, polyvinylidene fluoride, and polyvinylidene chloride. Examples include transparent or colored plastic films such as vinyl, nylon, polyacrylic acid, and polymethacrylic acid, woven fabric, nonwoven fabric, paper, metal foil, and vapor-deposited foil. In addition, if it is a material that can secure the function of the double-sided adhesive sheet,
There is no restriction whatsoever to use.

When transparency is required, among the above-mentioned base materials of the double-sided pressure-sensitive adhesive sheet, an olefin-based film such as polyethylene or polypropylene, a polyethylene terephthalate film or the like has a light transmittance of 75% or more. Plastic films can be used as substrates.

The pressure-sensitive adhesive layer in the present invention is a layer made of a pressure-sensitive rubber-based resin and having a thickness of about 5 to 100 μm. The adhesive rubber-based resin is a rubbery region in the temperature range at the time of use, and has a 180 ° peeling adhesive strength of 50 according to the adhesive tape / adhesive sheet test method specified in JIS Z0237.
gf / 25 mm or more, more preferably 500 gf / 25
There is no limitation as long as the holding force according to the test method exhibits adhesive properties of 60 minutes or more before dropping. The glass transition point (hereinafter referred to as Tg) of the adhesive rubber-based resin is −10.
C. or lower, more preferably in the range of -90.degree. C. or higher and -20.degree. C. or lower.

Specific examples of the adhesive rubber-based resin include an adhesive acrylic resin, natural and synthetic cis-1,4-polyisoprene rubber, butyl rubber, halogenated butyl rubber,
Partially vulcanized butyl rubber, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-
Ethylene-butylene-styrene block copolymer (S
EBS), silicone rubber, chloroprene rubber, nitrile rubber, butadiene rubber, and the like, which are generally used as pressure-sensitive adhesive resins, may be used.

In particular, the pressure-sensitive adhesive acrylic resin can change the Tg freely by appropriately setting the composition and molecular weight, is excellent in transparency and weather resistance, and is suitable for the pressure-sensitive adhesive layer of the present invention. It is. More specifically, the adhesive acrylic resin is mainly composed of a monomer component such as butyl acrylate or 2-ethylhexyl acrylate whose homopolymer has a Tg of −20 ° C. or less, a hydroxyl group, a tertiary amino group, a carboxyl group, and an amide. Component having a functional group such as a nitrile group, a nitrile group, and Tg for imparting cohesive strength
Is a resin obtained by copolymerizing a monomer component having a temperature of 20 ° C. or higher, and is generally used as an acrylic resin for an adhesive.

That is, the adhesive acrylic resin refers to one or several kinds of monomers having a functional group such as a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group, a nitrile group, and an alkyl (meth) acrylate, vinyl acetate. ,
Copolymers with monomers such as vinyl propionate, vinyl ether and styrene. Examples of the adhesive containing an adhesive acrylic resin include Olivine BPS3156D, BPS3180-3A, and BPS3180-3A manufactured by Toyo Ink Mfg. Co., Ltd.
PS3713, BPS4891, BPW5689J, B
PW5320 and the like.

The adhesive acrylic resin is synthesized by ordinary radical polymerization. There is no particular limitation on the synthesis method, and it can be synthesized by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc., but the solution polymerization is performed because the reaction can be easily controlled and the process can be directly transferred to the next operation. Is preferred.
As the solvent at the time of polymerization, methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate,
Any material, such as butyl acetate, can be used as long as the resin of the present invention can be dissolved. A single solvent may be used, or a plurality of solvents may be mixed.

The polymerization initiator used in the polymerization reaction may be an organic peroxide such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, or an azo-based initiator such as azobisisobutyronitrile. Any known agent such as an agent may be used, and there is no particular limitation. Adhesive acrylic resin is
It is also possible to partially crosslink using a curing agent such as an isocyanate and an epoxy compound or a metal chelate to improve the cohesive force before use.

In the pressure-sensitive adhesive layer of the present invention, a pigment, a dye, and
An inorganic filler, a metal powder such as silver powder, copper powder, and nickel powder, a tackifier such as a xylene resin, a terpene-based resin, and a rosin-based resin, and a silane coupling agent can be added. When transparency is required, among the above-mentioned adhesives, an adhesive such as an adhesive acrylic resin or an adhesive polyurethane resin is used in such a thickness that the light transmittance becomes 75% or more. be able to.

The non-adhesive layer in the present invention is a layer having substantially no adhesiveness when adhered to an adherend or having an adhesive property capable of being peeled off with a small stress. There is no limitation as long as the shape is such that a part of the pressure-sensitive adhesive layer can be exposed over the entire surface on the surface in contact with the adherend after lamination. Specifically, coarse woven fabric and nonwoven fabric with holes, powder, microcapsules,
A resin layer patterned by partially printing or the like can be used, but a patterned resin layer is preferable because it allows fine adjustment of the area ratio of the non-adhesive layer and the design of the pattern shape.

As the woven cloth, a general cloth such as gauze is used. Specifically, 40 pieces of woolen fabric / inch × 28 pieces / inch woolen thread 40/1 (manufactured by Aoyama Sangyo Co., Ltd.), 45 pieces of woolen fabric / inch × 35 pieces / inch
Sufu yarn 30/1 (manufactured by Aoyama Sangyo Co., Ltd.), polyethylene terephthalate (hereinafter referred to as PET) woven cloth 45 / inch × 35 / inch PET80d special yarn × 100d
Processed yarn (manufactured by Aoyama Sangyo Co., Ltd.), PET woven 45 / inch × 30 / inch PET80d special yarn × 100d
Processed yarn (manufactured by Aoyama Sangyo Co., Ltd.) and the like. Also,
As a nonwoven fabric with holes, a 50% nonwoven fabric of rayon (basis weight 10 g / m2, manufactured by Daio Paper Co., Ltd.), a nonwoven fabric of 50% rayon (basis weight 17 g / m2, manufactured by Daio Paper Co., Ltd.), a 50% nonwoven fabric of rayon (basis weight 30 g) / M2, manufactured by Daio Paper Co., Ltd.), 70% non-woven fabric of vinylon (100 μm, manufactured by Daio Paper Co., Ltd.), 100% non-woven fabric of vinylon (100 μm, manufactured by Daio Paper Co., Ltd.), polyester nonwoven fabric, etc. .

Specific examples of the powder include silicon dioxide typified by aluminum, copper, silver, gold, and aerosil;
Titanium dioxide, shirasu, diatomaceous earth and other metal and metal oxide fine particles, nylon powder, polyethylene powder, polymer microspheres such as polystyrene beads and acrylic beads, edible powders such as flour and starch, about tens to hundreds of micrometers A powder having a particle size is exemplified. Examples of microcapsules include JP-B-38-19574, JP-B-42-446, JP-B-42-771, JP-B-42-2882, and JP-B-42-28.
No. 83, Japanese Patent Publication No. 56-115371, Japanese Patent Publication No. 60-60173, and the like.
Japanese Patent Publication No. 36-9168, US Pat. No. 3,427,250, BP 1236498, etc.
situ polymerization method, US Pat. No. 3,787,327, US Pat.
P3551346, US Pat. No. 3,574,133, and the like.
No. 7, US Pat. No. 2,800,458, US Pat.
No. 1418, US Pat. No. 3,577,515, BP1
Coacervation method (phase separation method) described in US Pat. No. 117178, US Pat. No. 3,523,906, US Pat.
An interface precipitation method described in P3660304 and the like,
Microcapsules obtained by a spray drying method or the like described in US Pat. No. 3,830,750, etc., and hollow glass spheres and shirasu described in "New Edition Microcapsules-Manufacturing Methods, Properties, and Applications" by Tamotsu Kondo and Masazumi Koishi (Sankyo Shuppan). Balloons, alumina bubbles, phenol microballoons and the like, which are fine hollow spheres obtained by heating and foaming.

The patterned resin layer is a gravure,
Using a printing method such as silk screen, offset, flexo, ink jet, or thermal transfer, the resin is striped, latticed, polka dot, inverted polka dot, staggered pattern, etc., or design with information such as characters and symbols. Is formed by printing in various patterns. At this time, if the non-adhesive layer is printed so that a part of the adhesive layer is exposed over the entire surface when the adhesive layer is laminated without being solid printed, any pattern or printing method can be used. The present invention is not limited at all.

More specifically, a stripe refers to a pattern in which the printed portion of the resin has a width in the range of 50 μm to 10 mm, and the interval between the stripes has a range in the range of 50 μm to 50 mm. 90 kinds of stripes
A pattern that crosses at an angle of degrees.
There is no limitation on a pattern that is deformed from 0 degrees to 80 degrees (the smaller the angle of intersection). Further, a stripe or a lattice pattern having a plurality of line widths and an interval between the plurality of stripes may be used.

A polka dot means that the printed portion of the resin is in the range of 50 μm to 10 mm in diameter, and the distance between polka dots (between the centers of circles) is one.
A pattern that is arranged in a close-packed manner in the range of 0 μm to 50 mm is referred to. A negative polka dot pattern (a portion where the resin is not printed, the above polka dot pattern) in this range is called an inverted polka dot. In addition, polka dots and reverse polka dots having a plurality of diameters and a random arrangement may be used. The staggered pattern means a pattern in which one unit is in the range of 50 μ to 50 mm.

The shape of the pattern used when transparency is required is more specifically as follows. In the case of polka dots, the printed portion of the resin is in the range of 0.1 to 3 mm in diameter, and the distance between the polka dots (center between circles) is 10
It is a close-packed arrangement in the range of μ to 5 mm,
The negative polka dot may be a negative type of the polka dot pattern in this range (the portion where no resin is printed is the above polka dot pattern). In addition, polka dots and reverse polka dots having a plurality of diameters and a random arrangement may be used. In the case of the staggered pattern, the pattern as one unit is in the range of 0.1 mm to 5 mm.

In the case of stripes, the printed portion of the resin has a width in the range of 0.1 mm to 3 mm, and the interval between the stripes is in the range of 0.3 mm to 2 mm. In the case of a lattice, two types of stripes in the above range are crossed at an angle of 90 degrees, but the crossing angle is changed from 30 degrees to 80 degrees (the smaller crossing angle is smaller). The pattern is not limited at all. Also, various types of line widths and intervals between various types of stripes may be used at the same time.

In any case, the area ratio between the adhesive layer and the non-adhesive layer is from 90:10 to 10:90, and the pattern of the non-adhesive layer is composed of a minimum repeating unit having an area of 5 mm × 5 mm or less. However, it is preferable in patterning used for a double-sided pressure-sensitive adhesive sheet requiring transparency. When the area ratio of the non-adhesive layer exceeds 90%, the 180-degree peeling adhesive force is extremely reduced to about 50 gf / 25 mm, and thus does not function as a double-sided adhesive sheet in practical use. When the area ratio of the non-adhesive layer is less than 10%, the air bubble removing property at the time of sticking work becomes extremely poor, and the surface smoothness cannot be obtained due to blistering of the sheet due to the remaining air bubbles, and the transparent layer is not transparent. In applications where the properties are required, problems such as a decrease in transparency due to residual bubbles arise. Also, 5mm ×
When the non-adhesive layer is patterned with the area exceeding 5 mm as the minimum repeating unit, the air bubble removal property when the double-sided pressure-sensitive adhesive sheet is adhered and applied becomes insufficient, and the residual air bubbles become noticeable in some places, and the transparency is impaired. It is.

Examples of the resin constituting the non-adhesive layer include resins such as acrylic resin, polyester resin, polyurethane resin, silicone resin, epoxy resin, vinyl resin, nitrified cotton, and polyolefin resin. In particular, an acrylic resin is suitable as a resin constituting the non-adhesive layer of the present invention because it can freely set the structure and the molecular weight to freely change the Tg. In addition, a plurality of resins can be mixed and used. As the resin constituting the non-adhesive layer,
In order to form a layer that does not substantially exhibit adhesiveness when adhered to an adherend or has an adhesive property that can be peeled off with a weak stress, the Tg is in a range of 0 ° C. or more, and further, 10 ° C. or more and 110 ° C. or less. Are preferred. If the Tg is less than 0 ° C., a tackiness occurs in an environment of 20 ° C. or more, causing a phenomenon of adhesion to an adherend by blocking, etc., and the adhesion as a non-adhesive layer is impaired. In addition, inconveniences such as a transition from a printed surface after printing and winding to a surface in contact after winding and the like occur. On the other hand, when Tg exceeds 110 ° C., flexibility at around 20 ° C. is insufficient, and phenomena such as cracking when bent are caused.

Further, the resin constituting the non-stick layer is 5
When laminated on a PET film having a thickness of 0 μm so as to have a dry film thickness of 50 μm, the 180 ° peeling adhesive strength according to the adhesive tape / adhesive sheet test method specified in JIS Z0237 is less than 10 gf / 25 mm immediately after application, Further, it is preferably 0 gf / 25 mm or more and less than 10 gf / 25 mm. 180 degree peeling adhesive strength 10g
When it is f / 25 mm or more, it is difficult to sufficiently exhibit the function as a non-adhesive layer.

More specifically, as the acrylic resin constituting the non-adhesive layer, there may be used an acrylic resin solution such as Dianal LR-016 (Tg: 19 ° C.), manufactured by Mitsubishi Rayon Co., Ltd.
-1215 (Tg: 20 ° C.), LR-188 (Tg: 2
0 ° C), LR-331 (Tg: 20 ° C), LR-216
(Tg: 26 ° C), LR-194 (Tg: 29 ° C), L
R-574 (Tg: 31 ° C), LR-689 (Tg: 3)
3 ° C.), LR-637 (Tg: 42 ° C.), LR-472
(Tg: 46 ° C), LR-170 (Tg: 48 ° C), L
R-396 (Tg: 50 ° C.), LR-167 (Tg: 5
2 ° C), LR-162 (Tg: 52 ° C), LR-117
3 (Tg: 53 ° C), LR-163 (Tg: 55 ° C),
LR-1307 (Tg: 56 ° C), LR-214 (T
g: 57 ° C), LR-177 (Tg: 60 ° C), LR-
001 (Tg: 60 ° C.), LR-158 (Tg: 65
° C), LR-510 (Tg: 65 ° C), LR-143
(Tg: 66 ° C), LR-485 (Tg: 67 ° C), L
R-186 (Tg: 77 ° C.), LR-469 (Tg: 7)
7 ° C.), LR-90 (Tg: 85 ° C.), LR-1306
(Tg: 94 ° C), LR-248 (Tg: 102 ° C),
LR-1065 (Tg: 105 ° C), LR-343 (T
g: 105 ° C), LR-269 (Tg: 105 ° C), L
R-174 (Tg: 108 ° C.) and the like.

A bead resin BR-50 (Tg: 100) made of beaded acrylic resin manufactured by Mitsubishi Rayon Co., Ltd.
° C), BR-52 (Tg: 105 ° C), BR-60 (T
g: 75 ° C), BR-64 (Tg: 55 ° C), BR-7
3 (Tg: 100 ° C), BR-75 (Tg: 90 ° C),
BR-77 (Tg: 80 ° C.), BR-79 (Tg: 35)
° C), BR-80 (Tg: 105 ° C), BR-83 (Tg
g: 105 ° C), BR-85 (Tg: 105 ° C), BR
-87 (Tg: 105 ° C), BR-88 (Tg: 105
° C), BR-90 (Tg: 65 ° C), BR-93 (T
g: 50 ° C), BR-95 (Tg: 80 ° C), BR-1
00 (Tg: 105 ° C.), BR-101 (Tg: 50)
° C), BR-102 (Tg: 20 ° C), BR-105
(Tg: 50 ° C), BR-106 (Tg: 50 ° C), B
R-107 (Tg: 50 ° C), BR-108 (Tg: 9)
0 ° C), BR-112 (Tg: 20 ° C), BR-113
(Tg: 75 ° C), BR-115 (Tg: 50 ° C), B
R-116 (Tg: 50 ° C.), BR-117 (Tg: 3
5 ° C.) and BR-118 (Tg: 35 ° C.).

As the polyester resin constituting the non-adhesive layer, Toyobo Co., Ltd. Byron 130 (Tg: 1)
3 ° C.), Byron 200 (Tg: 67 ° C.), Byron 3
00, Byron 500, Byron 530, Byron GM
400, Byron GV100, Byron GV700 and the like. Examples of the polyurethane resin include a non-yellowing type TPU series manufactured by Asahi Kasei Kogyo Co., Ltd., etc., examples of the nitrified cotton include those manufactured by Asahi Kasei Kogyo Co., Ltd., and examples of the polyolefin resin include the Sumikasen series manufactured by Sumitomo Chemical Co., Ltd.

From the viewpoint of printability such as gravure printing, gravure inks containing a urethane resin, such as "Ramister R Medium", "New LP Super", and "LP Queen" series manufactured by Toyo Ink Manufacturing Co., Ltd. are used. Can also. Furthermore, when printing these resins, improve various properties such as coating suitability by adding inorganic fillers and organic compounds including aerosil, barium sulfate, a silicon-based leveling agent, aluminum chelate A, and polyisocyanate. Is possible. In addition, it is also possible to add a deterioration inhibitor such as an ultraviolet absorber for the purpose of improving the weather resistance of the resin.

When transparency is required, the non-adhesive layer may be formed of a resin such as an acrylic resin, a polyester resin, a nitrified cotton, or a polyvinyl acetal resin among the above-mentioned resins. It can be used in such a thickness that the transmittance is 75% or more.

The release paper is used as a base material for printing the non-adhesive layer, and the non-adhesive layer is printed on the release-treated surface of the release paper. After laminating the non-adhesive layer and the adhesive layer, the adhesive force at the non-adhesive layer-release paper interface must be smaller than the adhesive force at the adhesive layer-non-adhesive interface. At the same time, at the interface between the pressure-sensitive adhesive layer and the release paper, it is required that the release paper can be easily peeled when the release paper is released, and that the pressure-sensitive adhesive layer does not remain on the release paper. The level that can be easily peeled here means that the 180-degree peeling adhesive force at a peeling speed of 300 mm per minute between the release paper and the adhesive sheet is generally less than 100 gf / 25 mm, and more preferably 3 gf / 25 mm. More than 50gf / 2
5 mm or less.

Examples of the release paper include various plastic films such as PET and oriented polypropylene (OPP) or paper coated with a silicone-based or non-silicone-based release agent. Examples include a company-made binder series, a binder sheet series, a Tocelo separator SP series made by Tocelo Co., Ltd. and a kite chemical company TSM-110K.

The method for applying the pressure-sensitive adhesive layer on the substrate is as follows.
There is no limitation as long as the method can be used to form a thin film layer of about 100 μm. Specifically, it is performed using a comma coater, a lip coater, a kiss coater, or the like. That is, it is not different from a general production method of an ordinary pressure-sensitive adhesive sheet.
The method of laminating the non-adhesive layer on the pressure-sensitive adhesive layer is a method in which the surface of the pressure-sensitive adhesive sheet in contact with the adherend can be divided into an adhesive layer portion and a non-adhesive layer portion. There is no restriction to use any method as long as the non-stick layer can be laminated so that part of the layer is exposed over the entire surface.

Specifically, when the non-adhesive layer is in the form of a sheet such as a woven fabric, a perforated nonwoven fabric, or a patterned resin layer, each of the adhesive layers coated on both surfaces of the substrate is used. And the sheet-shaped non-adhesive layer can be laminated by laminating using the adhesive force on the surface of the pressure-sensitive adhesive layer. When the non-adhesive layer is in the form of powder, microcapsules, or other fine particles, the surface of the adhesive layer coated on both sides of the substrate is sprayed or sieved to partially treat the surface of the adhesive layer one by one. Can be laminated.

Further, when the non-adhesive layer is a patterned resin layer, the non-adhesive layer is patterned on release paper, and an adhesive is directly applied thereon to laminate the adhesive layer. Can be. According to this method, the pressure-sensitive adhesive layer and the non-adhesive layer form substantially the same plane on the surface in contact with the adherend, and a smooth surface state can be realized. A transfer-type double-sided pressure-sensitive adhesive sheet (transfer tape) composed of a pressure-sensitive adhesive layer and a non-pressure-sensitive layer by using release paper as a base material when forming the non-pressure-sensitive layer and peeling the release paper at the time of use It is also possible to use When the surface in contact with the adherend is smooth, the pressure-sensitive adhesive layer and the non-adhesive layer uniformly contact the substrate supporting the pressure-sensitive adhesive layer. Does not adversely affect Furthermore, it becomes difficult for foreign substances such as moisture, air, dust, and dust to enter from the end face, and at the same time, the air and moisture mixed in the adhesive sheet are extruded in one direction by a squeegee or the like, thereby forming the non-adhesive layer. The passage can be easily removed to the outside of the adhesive sheet (air release property).

A more specific method for producing the double-sided PSA sheet of the present invention is described below. When laminating an adhesive layer and a non-adhesive layer on both sides of the substrate, two (release paper / non-adhesive layer / adhesive layer) prepared in advance by the above method are laminated on both sides of the substrate, respectively. Thereby, a double-sided pressure-sensitive adhesive sheet having a structure of (release paper / non-adhesive layer / pressure-sensitive adhesive layer) / substrate / (pressure-sensitive adhesive layer / non-adhesive layer / release paper) can be obtained. When laminating an adhesive layer and a non-adhesive layer on one side of a base material, it is based on (release paper / non-adhesive layer / adhesive layer) and (release paper / adhesive layer) prepared in advance by the above method. By laminating on both sides of the material, (release paper / non-adhesive layer / adhesive layer)
/ Substrate / (pressure-sensitive adhesive layer / release paper) can be obtained.

As for the transfer type sheet, a non-adhesive layer is patterned on a release paper, an adhesive is directly applied thereon, and after drying, the patterned non-adhesive layer is separately prepared on a release paper. , Laminated on the pressure-sensitive adhesive layer surface, (release paper / non-adhesive layer / pressure-sensitive adhesive layer) / (non-adhesive layer / release paper)
Can be obtained. In this case, a transfer-type double-sided pressure-sensitive adhesive sheet (transfer tape) having different adhesive strengths on one surface and the other surface can be obtained by changing the pattern, the area, and the like of the non-adhesive layer patterned on the release paper.

The 180-degree peeling adhesive strength of the double-sided pressure-sensitive adhesive sheet of the present invention can be adjusted by changing the area ratio of the pressure-sensitive adhesive layer and the non-adhesive layer in contact with the adherend. In the present method, by increasing the area ratio of the non-adhesive layer, the actual adhesive area to the adherend is reduced to reduce the 180-degree peeling adhesive force, and the area ratio of the non-adhesive layer is reduced. By lowering it, the adhesive area is increased and the adhesive strength is increased by 180 ° peeling. When the non-adhesive layer is a patterned resin layer, it is possible to adjust the peeling force by 180 degrees by changing the pattern to be printed and its area. For example, when printing a polka dot plate, even if the same pressure-sensitive adhesive layer is used in the area ratio with respect to the entire polka dot portion, the polka dot diameter, the polka dot arrangement method, etc., a double-sided pressure-sensitive adhesive sheet having a completely 180 ° peeling adhesive force is completely different. can get.

More specifically, the pressure-sensitive adhesive layer alone contains 1500
When using a pressure-sensitive adhesive having a peel strength of 180 ° of about gf / 25 mm as the pressure-sensitive adhesive layer, and forming a non-adhesive layer in a polka dot pattern having a diameter of 0.5 mmφ in a close-packed arrangement corresponding to each area ratio. As an example, the relationship between the 180-degree peeling adhesive force and the area ratio of the adhesive layer and the non-adhesive layer will be described. Slight adhesive strength (1
80 degree peeling adhesive strength: 100-500gf / 25m
m)), the area ratio of the non-adhesive layer in the polka dot portion is preferably set to 70 to 90%.

Further, in order to develop a medium adhesive strength (180 ° peel adhesive strength: about 500 to 1200 gf / 25 mm), the area ratio of the non-adhesive layer in the polka dot portion should be 20 to 70%.
Is preferable. A delicate region from medium adhesive strength to strong adhesive strength can be adjusted by adjusting the area ratio in the range of 10 to 20%.

The double-sided pressure-sensitive adhesive sheet of the present invention is required to have a highly versatile medium pressure-sensitive adhesive strength and adhesion reliability from a slight pressure-sensitive adhesive force for re-peeling applications, utilizing the fact that the 180-degree peeling force can be freely adjusted. It can be used for a wide range of applications up to strong adhesive strength. Furthermore, a smooth adhesive sheet having a 180-degree peel-off adhesive strength such as a slightly adhesive area and having a flat surface in contact with the adherend (the surface of the adhesive layer and the non-adhesive layer) without any step is the same as the adhesive sheet. It has good air bleeding property at the time of sticking work and has a smooth surface on the base material, and is most suitable for marking films used for signs and the like. Other specific applications that take advantage of the features of the present invention include wide nameplate applications, printing plate fixing applications, polishing cloth fixing applications, and transparent substrates such as heat ray cut films and shatterproof films that are attached to window glass. For example, it can be used for sticking to materials, and for fixing materials related to building materials.

Further, by changing the area ratio of the non-adhesive layer on one side and the other side of the double-sided pressure-sensitive adhesive sheet, one side can be formed even though the same pressure-sensitive adhesive layer is used. It is possible to obtain a double-sided pressure-sensitive adhesive sheet having strong adhesive force and different adhesive force on one surface and the other surface such that the other surface has a slight adhesive force.
The double-sided pressure-sensitive adhesive sheet is used for limiting the peeling surface when peeling after bonding to a specific surface, that is, for temporarily attaching a poster to a bulletin board, a label to be used for promotion to a product, fixing a sanitary napkin, or the like. Ideal for re-stripping applications.

[0048]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight”. In addition, Tg of the resin was measured from a temperature range of -100 ° C. to 200 ° C. at a heating rate of 10 ° C./min using a DSC manufactured by Seiko Electronics Co., Ltd., and was measured from an endothermic peak.
When a plurality of peaks were present, the value of the larger endothermic peak was adopted. The 180-degree peel strength of the non-adhesive layer with respect to the test plate is determined by dissolving the resin constituting the non-adhesive layer to a suitable concentration in a solvent such as ethyl acetate or toluene that can dissolve the resin. 5 so that it becomes 50μ
Cast on a 0μ thick PET film to JIS Z0
237. That is, a resin layer coated on a 50 μPET base material with a thickness of 50 μm is formed to a width of 25 mm and a length of 150 μm.
mm, and attached to a stainless steel plate (SUS304) polished with # 280 sandpaper and allowed to stand for 30 minutes. Then, at a temperature of 25 ° C. and a relative humidity of 60%, 180 ° at a peeling speed of 300 mm / min. The peel adhesion was measured.

(Synthesis of Adhesive Resin) Adhesive Resin 1 108.0 parts of polyester polyol (“P-1010” manufactured by Kuraray Co., Ltd.) 67.0 parts of polyether polyol (“G-2000” manufactured by Asahi Denka Co., Ltd.) Hexamethylene diisocyanate (Sumitomo Bayer K.K.) 25.0 parts Toluene 134.0 parts 2-Ethylhexaneiron 0.03 parts Lead naphthenate 0.04 part The above was heated to 90 ° C. in a nitrogen atmosphere using a flask as a reaction vessel. The mixture having the composition was heated and stirred for 4 hours, and then cooled to obtain a solution of the pressure-sensitive adhesive resin 1 (solid content: 60% by weight).

Pressure-sensitive adhesive resin 2 Butyl acrylate 93.1 parts Acrylic acid 6.9 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts The above was heated to 80 ° C. in a nitrogen atmosphere using a flask as a reaction vessel. 125 parts of the mixture of the composition were mixed with the mixture 12 of the same composition.
Five parts were added dropwise, and after the completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a pressure-sensitive adhesive resin solution (solid content: 40% by weight).
A mixture of the following composition containing the obtained pressure-sensitive adhesive resin solution was stirred at room temperature in a nitrogen atmosphere for 1 hour to obtain a pressure-sensitive adhesive resin 2 solution (solid content: 40% by weight). Polymerized rosin-based tackifier 40.0 parts (“Dimalex resin” manufactured by Rika Hercules Co., Ltd.) Toluene 60.0 parts Solution of the above adhesive resin 300.0 parts

Example 1 Acrylic resin solution (“LR331” manufactured by Mitsubishi Rayon Co., Ltd., Tg: 20 ° C., 180
(Peeling strength: 0 gf / 25 mm) was adjusted in viscosity with ethyl acetate to obtain a coating liquid (solid content: 20% by weight). PE
T release paper (“SP-PET-D13-
50-BU ”) on the peeling surface so that the application amount is 0.5 g / m ^{2 in} a pattern with a polka dot diameter of 0.5 mmφ and an area ratio (ratio to the entire polka dot printed portion) of 30% as shown in FIG. The obtained coating liquid was subjected to gravure printing to laminate a non-adhesive layer. Next, an adhesive containing an adhesive acrylic resin (“Oribine BPS3156D” manufactured by Toyo Ink Mfg. Co., Ltd., T
g: -40 ° C.) and 100 parts of a tolylene diisocyanate derivative-based curing agent (“BHS85” manufactured by Toyo Ink Mfg. Co., Ltd.)
15 ") The coating liquid obtained by stirring and mixing 3 parts was applied with a comma coater so as to have a dry film thickness of 30 µm, and the pressure-sensitive adhesive layer was laminated. At the time of winding, 3 kg of a 12 µm thick PET film was wound.
By laminating under a pressure of f / cm ^2, a first surface side composed of release paper / non-adhesive layer / adhesive layer / substrate was prepared. A release paper / non-adhesive layer / adhesive layer is laminated with the same material, composition and method to produce the second side, and finally the base material on the first side and the adhesive on the second side are removed. Laminate and release paper (1st side)
Non-adhesive layer / adhesive layer / substrate / adhesive layer / non-adhesive layer /
A double-sided pressure-sensitive adhesive sheet 1 having a cross section shown in FIG. 1 having a configuration of a release paper (second surface side) was obtained.

(Examples 2 to 5, 9 to 12)
In Nos. 3 and 11, the release paper / non-adhesive layer / adhesive layer / substrate / adhesive layer / non-adhesive layer / peeling shown in Tables 1 and 2 (on the first side) was performed in the same manner as in Example 1. Double-sided PSA sheets 2-3 having the cross section shown in FIG. 1 were obtained with the paper (second surface side) configuration. Here, regarding the patterns of the non-adhesive layer shown in Tables 1 and 2, the polka dot indicates the shape of FIG. 6, the reverse polka dot indicates the shape of FIG. 7, and the lattice indicates the shape of FIG.
The area ratio indicates the ratio of the printed portion to the whole. Further, in Examples 4 and 10, since the non-adhesive layer has a structure only on the first surface, a release paper is used instead of the release paper / non-adhesive layer / adhesive layer used in the preparation of the second surface in Example 1. / Using the pressure-sensitive adhesive layer, double-sided pressure-sensitive adhesive sheets 4 and 10 having the cross section shown in FIG. 2 were obtained. Further, in Examples 5, 9, and 12, the transfer type structure without the base material is used. Therefore, instead of the base material lamination in the final stage of laminating the first surface in Example 1, the second surface prepared in advance is used. Were laminated to obtain double-sided PSA sheets 5, 9, and 12 having the cross section shown in FIG.

(Example 6) An adhesive containing an adhesive acrylic resin ("Oribine BPW5320" manufactured by Toyo Ink Mfg. Co., Ltd., Tg: -4) on a PET film having a thickness of 25 µm.
(5 ° C.) with a comma coater so as to have a dry film thickness of 30 μm to form an adhesive layer. Next, on the dried surface of the pressure-sensitive adhesive layer, 40 nonwoven fabrics of Aoyama Sangyo Co., Ltd./inch×28 yarns / inch 40/1 yarn are laminated to form a non-adhesive layer. "TSM-110K" (trade name, manufactured by Co., Ltd.) was laminated at a pressure of 3 kgf / cm @ 2 to produce a first surface composed of release paper / non-adhesive layer / adhesive layer / substrate. Next, a pressure-sensitive adhesive layer was pressure-coated with a similar material, composition and method on release paper (“TSM-110K” manufactured by Kite Chemical Industry Co., Ltd.) to form a release paper /
The second side composed of the pressure-sensitive adhesive layer is prepared, and finally, the base material on the first side and the pressure-sensitive adhesive on the second side are laminated (the first side). Release paper / non-adhesive layer / adhesive A double-sided pressure-sensitive adhesive sheet 6 having a cross section shown in FIG. 4 was obtained in the configuration of the agent layer / base material / pressure-sensitive adhesive layer / release paper (second side).

Example 7 An adhesive layer was laminated on a 25 μm thick PET film in the same manner as in Example 6. next,
After a hollow glass sphere ("Shirasu Balloon YO4" manufactured by Sanki Kako Co., Ltd.) is sifted over the dry surface of the adhesive layer, the excess hollow glass sphere is blown at a wind speed of 20 / sec.
After removing with a wind of M, a non-adhesive layer is laminated, and 3 kg of release paper (“TSM-110K” manufactured by Kite Chemical Industry Co., Ltd.) is further added.
By laminating under a pressure of f / cm ^2, a first surface side composed of release paper / non-adhesive layer / adhesive layer / substrate was prepared. next,
Release paper ("TSM-110" manufactured by Kite Chemical Industry Co., Ltd.)
K ") on the pressure-sensitive adhesive layer with the same material, composition and method to prepare a second surface side composed of a release paper / pressure-sensitive adhesive layer, and finally, the base material on the first surface side and the second surface side. Laminate the pressure-sensitive adhesive on the two sides (first side) and release paper / non-adhesive layer / pressure-sensitive adhesive layer / substrate /
A double-sided pressure-sensitive adhesive sheet 7 having the structure of pressure-sensitive adhesive layer / release paper (second surface side) and having a cross section shown in FIG. 5 was obtained.

Example 8 A non-adhesive layer was patterned on a release paper in the same manner as in Example 1 with the composition and composition shown in Table 2. Next, an adhesive containing an adhesive acrylic resin (“Olivine BPS3156D” manufactured by Toyo Ink Mfg. Co., Ltd., Tg: −40 ° C.) was placed on a 25 μm thick PET film.
Then, a coating liquid obtained by stirring and mixing 00 parts and 3 parts of a tolylene diisocyanate derivative-based curing agent (“BHS8515” manufactured by Toyo Ink Mfg. Co., Ltd.) is adhesively coated with a comma coater so as to have a dry film thickness of 30 μm. Were laminated. At the time of winding, 3 kgf / cm of PET release paper on which the non-adhesive layer is patterned so that the adhesive layer and the non-adhesive layer are in contact with each other.
^By laminating under a pressure of ^2, a first side composed of release paper / non-adhesive layer / adhesive layer / substrate was prepared. Next, a pressure-sensitive adhesive layer was laminated on the other surface of the first substrate in the same manner as above. At the time of winding, a PET release paper on which a non-adhesive layer is patterned is laminated at a pressure of 3 kgf / cm ² so that the adhesive layer and the non-adhesive layer are in contact with each other (first pressure).
Surface side) Release paper / non-adhesive layer / pressure-sensitive adhesive layer / substrate / pressure-sensitive adhesive layer / non-adhesive layer / release paper (second surface side) to obtain double-sided pressure-sensitive adhesive sheet 8 having a cross section shown in FIG. .

(Comparative Example 1) Except that "PET release paper having a polka dot-shaped non-adhesive layer laminated thereon" was changed to PET release paper ("SP-PET-D13-50-BU" manufactured by Tosello Co., Ltd.) In the same manner as in Example 1, a double-sided PSA sheet 13 having the composition and configuration shown in Table 3 was obtained.

(Comparative Example 2) An adhesive containing an adhesive acrylic resin ("Oribine BPS3713" manufactured by Toyo Ink Mfg. Co., Ltd., Tg) was applied to the release surface of a release paper ("TSM-110K" manufactured by Kite Chemical Industry Co., Ltd.). A coating liquid obtained by stirring and mixing 100 parts of -43 ° C) and 3 parts of a tolylene diisocyanate derivative-based curing agent (“BHS8515” manufactured by Toyo Ink Mfg. Co., Ltd.) was applied with a comma coater by adhesive coating so as to have a dry film thickness of 30μ. Pressure-sensitive adhesive layer, and release paper at the time of winding (“TSM-110K” manufactured by Kite Chemical Industry Co., Ltd.)
Was laminated at a pressure of 3 kgf / cm ² to obtain a double-sided PSA sheet 14.

(1) Evaluation of 180-degree Peeling Adhesive Strength For the double-sided pressure-sensitive adhesive sheets 1 to 10 from which the release paper was peeled, J
The 180-degree peel adhesive force was measured by the adhesive tape / adhesive sheet test method specified in IS Z0237.
Specifically, after laminating a 50 μPET film on the second surface side, cut into a width of 25 mm and a length of 150 mm.
80 sanded stainless steel plate (SU
After sticking the first side to S304) and leaving it for 30 minutes,
At a temperature of 25 ° C. and a relative humidity of 60%, a peeling speed of 300
The adhesive force was peeled off at 180 ° at mm / min, and the peeling state at that time was observed. The results are shown in Table 4.

(2) Evaluation of Surface State of Adhesive Sheet After Adhesion For the double-sided adhesive sheets 1 to 10 from which the release paper was peeled,
The release paper of the double-sided pressure-sensitive adhesive sheet cut into a width of 150 mm and a length of 150 mm is peeled off, and a 50 μPET film is adhered to each of the first and second surfaces and pressed with a squeegee, and the state of the surface is visually observed. did. The results are shown in Table 4.

(3) Measurement of Light Transmittance The light transmittance was measured by using a spectrophotometer (“U-
best 30 ”), and the light transmittance was compared with air at 400 to 700 nm without inserting anything on the reference side, and the minimum value in this range was recorded. The results are shown in Table 4.

(4) Evaluation of Transparency The pressure-sensitive adhesive sheet was cut into a size of 150 mm × 150 mm, the release paper on the first side was peeled off, and the pressure-sensitive adhesive sheet was attached to a transparent glass plate having a thickness of 2 mm using a squeegee while removing air bubbles. Then, the release paper on the second surface was peeled off, and the transparency was visually evaluated. The results are shown in Table 4.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

Remarks PET Sepa: PET release paper (“SP-PET-D13-50-BU” manufactured by Tosero Corporation) Paper Sepa: Release paper (TSM- manufactured by Kite Chemical Industry Co., Ltd.)
110K ") Rayon nonwoven fabric: 50% rayon nonwoven fabric (basis weight 17g /
m ^2, Daio Paper Co., Ltd.) LR331: Mitsubishi Rayon Co., Ltd., acrylic resin BR64: Mitsubishi Rayon Co., Ltd., acrylic resin S-LEC BM-5: Sekisui Chemical Co., Ltd. butyral resin HI2000: Asahi Kasei Co., Ltd. nitrification cotton BPS3156D: oriental Adhesive containing adhesive acrylic resin manufactured by Ink Manufacturing Co., Ltd. BHS8515: Tolylene diisocyanate derivative-based curing agent manufactured by Toyo Ink Manufacturing Co., Ltd. Byron 200: Polyester resin manufactured by Toyobo Co., Ltd. BPS3180-3A: Adhesive manufactured by Toyo Ink Manufacturing Co., Ltd. Adhesive containing acrylic resin BPS3180B: aliphatic isocyanate derivative-based curing agent manufactured by Toyo Ink Manufacturing Co., Ltd.

[0066]

[Table 4]

[0067]

According to the present invention, a double-sided pressure-sensitive adhesive sheet capable of peeling 180 degrees over a wide range to adjust the pressure-sensitive adhesive force by a simple structure of partially laminating a non-adhesive layer on the surface of the pressure-sensitive adhesive layer is provided. Can now be obtained. In the double-sided pressure-sensitive adhesive sheet of the present invention, it is possible to limit the peeling interface to one of the surfaces by adjusting the adhesive force between one surface and the other surface. In addition, the surface provided with the non-adhesive layer has good air bleeding property after adhesion to the adherend, and the surface of the base material becomes smooth, so that the design is not impaired. Further, by using a transparent resin, a base material, and an adhesive, a double-sided adhesive sheet having high transparency can be obtained.

[0068]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of the pressure-sensitive adhesive sheets of Examples 1 to 3 and 8.

FIG. 2 is a cross-sectional view of the pressure-sensitive adhesive sheets of Examples 4 and 10.

FIG. 3 is a sectional view of the pressure-sensitive adhesive sheets of Examples 5, 9 and 12.

FIG. 4 is a sectional view of the pressure-sensitive adhesive sheet of Example 6.

FIG. 5 is a sectional view of the pressure-sensitive adhesive sheet of Example 7.

FIG. 6 is a polka dot print pattern (hatched portion) in the non-adhesive layer of the pressure-sensitive adhesive sheets of Examples 1 to 3, 5, 8 and 11.

FIG. 7 shows a reverse polka dot printing pattern (hatched portion) in the non-adhesive layer of the adhesive sheet of Example 4.

FIG. 8 shows a grid printing pattern (hatched portion) in the non-adhesive layer of the pressure-sensitive adhesive sheets of Examples 5 and 9 to 12.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Substrate (12 microPET film or rayon nonwoven fabric) 2 Adhesive layer 3 Non-adhesive layer (printing resin layer) 4 Release paper 5 Non-adhesive layer (Suf cloth) 6 Non-adhesive layer (Shirasu balloon)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hideyuki Takahashi 2-13-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. F-term (reference) 4F100 AK25 AK41 AK41C AK41E AT00A BA03 BA04 BA05 BA06 BA07 BA10C BA10D BA10E BA32.

Claims (16)

[Claims] 1. A double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer and a non-adhesive layer laminated on both sides of a substrate such that a part of the pressure-sensitive adhesive layer is exposed over the entire surface. 2. An adhesive layer and a non-adhesive layer are laminated on one surface of a substrate so that a part of the adhesive layer is exposed over the entire surface, and only the adhesive layer is formed on the other surface of the substrate. A double-sided pressure-sensitive adhesive sheet formed by laminating. 3. A double-sided pressure-sensitive adhesive sheet comprising a non-adhesive layer laminated on both sides of a pressure-sensitive adhesive layer such that a part of the pressure-sensitive adhesive layer is entirely exposed. 4. The double-sided pressure-sensitive adhesive sheet according to claim 1, wherein the non-pressure-sensitive layer is a patterned resin layer. 5. The non-adhesive layer has an area ratio between the adhesive layer and the non-adhesive layer of 90:10 to 10:90, and is 5 mm × 5 m
The double-sided pressure-sensitive adhesive sheet according to claim 4, which is a resin layer patterned in a minimum repeating unit having an area of m or less. 6. The pressure-sensitive adhesive layer having a 180-degree peeling adhesive strength,
The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the pressure-sensitive adhesive layer is adjusted by a non-pressure-sensitive layer. 7. When a non-adhesive layer is laminated on a polyethylene terephthalate film having a thickness of 50 μm so as to form a film having a dry film thickness of 50 μm, the non-adhesive layer has a thickness of less than 10 gf / 25 mm with respect to a test plate specified in JIS Z0237.
5. A peeling and peeling adhesive material.
The double-sided pressure-sensitive adhesive sheet according to the above. 8. The double-sided pressure-sensitive adhesive sheet according to claim 4, wherein the non-adhesive layer contains a resin having a glass transition point of 0 ° C. or higher. 9. The double-sided pressure-sensitive adhesive sheet according to claim 1, wherein an area ratio between the pressure-sensitive adhesive layer and the non-adhesive layer in contact with the adherend is different between one surface and the other surface. 10. The double-sided pressure-sensitive adhesive sheet according to claim 5, wherein the light transmittance of visible light is 75% or more. 11. The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 10, wherein the double-sided pressure-sensitive adhesive sheet is used for temporary fixing / removing. 12. The method according to claim 1, which is used for heat ray shielding.
The double-sided pressure-sensitive adhesive sheet according to any one of the preceding claims. 13. An anti-scattering application.
The double-sided pressure-sensitive adhesive sheet according to any one of the preceding claims. 14. The method for producing a double-sided pressure-sensitive adhesive sheet according to claim 1, wherein a non-adhesive layer patterned on release paper and a pressure-sensitive adhesive layer coated on a substrate are laminated. 15. A non-adhesive layer is patterned on a release paper, and a pressure-sensitive adhesive layer is applied thereon, so that the non-adhesive layer and the pressure-sensitive adhesive layer are substantially flush with each other on the surface in contact with the adherend. The method for producing a double-sided PSA sheet according to any one of claims 1 to 3. 16. The 180-degree peeling adhesive force is adjusted by changing the area ratio of the pressure-sensitive adhesive layer and the non-adhesive layer in contact with the adherend of the double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 10. how to.