JP2000328014A - Adhesive tape or sheet and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide an adhesive tape or sheet having flexibility, excellent followability to an adherend, and excellent cutability, and a method for producing the same. The present invention provides a pressure-sensitive adhesive layer formed on one surface of a urethane resin layer comprising 100 parts by weight of a polyol component and A part by weight of a polyisocyanate component having a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) of 220 to 550. A laminated pressure-sensitive adhesive tape or sheet, wherein A is represented by the following formula, and A = 100aX / Y (where a is a constant;
067 to 0.135, X is the hydroxyl value of the polyol component, Y is the weight% of the isocyanate group in the polyisocyanate component) The 2% elongation at 5 ° C and 35 ° C of 0.40 to 2.20 Kg / An adhesive tape or sheet having a width of 15 mm and an elongation at break of 50 to 300%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive tape or sheet excellent in flexibility, adherence to an adherend, cutting properties, coloring properties, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A so-called vinyl tape comprising a soft vinyl chloride resin as a base material and a pressure-sensitive adhesive layer laminated on one side thereof has flexibility, conformability to an adherend, cutability, electrical insulation and the like. Since it is excellent, and it is easy to color or provide weather resistance as needed, it is widely used for applications such as electrical insulating tapes, anticorrosion tapes, sealing tapes, and marking sheets.

[0003] Among them, the marking sheet is, for example,
Advertising stickers used for signs, billboards, shutters, windows, etc .; decorative striped stickers used for cars, motorcycles, motorboats, snowmobiles, etc .; widely used as display stickers used for traffic signs, information boards, etc. However, since it is required that the adherend conforms to irregularities and curved surfaces and does not shrink with the passage of time, the base material is formed by adding a plasticizer, a pigment, etc. to a vinyl chloride resin, and generally using a calendering method. In particular, a marking sheet or the like that requires high quality in weather resistance and strength is formed by a casting method (for example, Japanese Patent Publication No. 5-888).
No. 62).

[0004]

However, since vinyl chloride resin contains chlorine, if it is incinerated after use, dioxin is generated, which poses a problem in terms of environmental hygiene. There is a demand for an adhesive tape or sheet having properties similar to those of a vinyl tape.

For example, Japanese Patent Application Laid-Open No. 3-45672 discloses a marking film using a polyurethane film as a base material. The above polyurethane film contains tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate as isocyanate components. Since diisocyanates having a short distance between isocyanate groups, such as hexamethylene diisocyanate, are used, flexibility is insufficient, and followability to irregularities and curved surfaces of an adherend is insufficient.

Japanese Patent Application Laid-Open No. Hei 8-20750 discloses that the weight average molecular weight is 80,000 to 500,000,
The elution amount at 0 ° C or more and 10 ° C or less by the cross fractionation method is 45 to 80% by weight of the total resin amount, and the elution amount at 10 ° C to 70 ° C is 5 to 35% by weight of the total resin amount, and The elution amount below 1 ° C. is 1 to 30% by weight of the total resin amount, and 95 ° C.
The eluted amount below 125 ° C is 3 to 35% by weight of the total resin.
A marking film using a polypropylene resin as a base material is described. This polypropylene resin has the drawbacks that it is too soft, a glossy film cannot be obtained, and the obtained film is difficult to cut. Further, there is a drawback that the weather resistance is low, and the stabilizer can be used for only about two years even if a stabilizer is added.

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive tape or sheet having flexibility, excellent followability to an adherend, and excellent cutability in view of the above-mentioned drawbacks, and a method for producing the same.

Another object of the present invention is to provide a pressure-sensitive adhesive tape or sheet having excellent coloring properties and weather resistance, which can be suitably used as a marking tape or sheet, and a method for producing the same.

[0009]

According to a first aspect of the present invention, there is provided a urethane resin comprising 100 parts by weight of a polyol component and A part by weight of a polyisocyanate component having a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) of 220 to 570. A pressure-sensitive adhesive tape or sheet in which a pressure-sensitive adhesive layer is laminated on one surface of a layer, wherein A is represented by the following formula: A = 100aX / Y (where a is a constant; 0.067 to 0.135; X is the hydroxyl value of the polyol component, Y is the weight% of the isocyanate group in the polyisocyanate component.
2.20 kg / 15 mm width and elongation at break of 50 to 3
It is an adhesive tape or sheet characterized in that it is 00%.

The second invention relates to a polyisocyanate component A having 100 parts by weight of a polyol component and a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) of 220 to 570.
A pressure-sensitive adhesive tape or sheet in which a urethane resin layer composed of parts by weight, an olefin-based resin layer, and a pressure-sensitive adhesive layer are sequentially laminated, wherein A is represented by the following formula: A = 100aX / Y (where a is a Constant: 0.067 to 0.135, X is the hydroxyl value of the polyol component, Y is the weight% of isocyanate group in the polyisocyanate component.
2.20 kg / 15 mm width and elongation at break of 50 to 3
It is an adhesive tape or sheet characterized in that it is 00%.

A third aspect of the present invention is a process for obtaining a first laminate in which an adhesive layer is laminated on one surface of a first release paper, 100 parts by weight of a polyol component, a distance between crosslinking points (weight average molecular weight / A reactive resin composition comprising a polyisocyanate component A (parts by weight of isocyanate group) of 220 to 570 and a solvent is applied to a second release paper and dried, and a crosslink rate of 20 to 93 is applied to one surface of the second release paper. % Urethane resin layer is formed, and the first laminate is formed such that the pressure-sensitive adhesive layer of the first laminate is in contact with the urethane resin layer of the second laminate. A step of laminating the body and the second laminate to complete the reaction of the urethane resin, wherein the above A is represented by the following formula, is there. A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component) A step of obtaining a first laminate in which an adhesive layer and a first release paper are sequentially laminated on one surface of an olefin-based resin layer, 100 parts by weight of a polyol component, distance between crosslinking points (weight average molecular weight / number of isocyanate groups) ) Is 220-5
A reactive resin composition comprising 70 parts by weight of a polyisocyanate component A and a solvent is applied to a second release paper and dried, and a urethane resin layer having a crosslinkage of 20 to 93% is formed on one surface of the second release paper. A step of obtaining a formed second laminate, and the step of obtaining the first laminate and the second laminate so that the olefin-based resin layer of the first laminate is in contact with the urethane resin layer of the second laminate. The method for producing a pressure-sensitive adhesive tape or sheet according to the second aspect of the present invention is characterized by comprising a step of laminating the laminate and completing the reaction of the urethane resin, wherein A is represented by the following formula. A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component)

A fifth aspect of the present invention provides a step of obtaining a first laminate in which an adhesive layer and a first release paper are sequentially laminated on one surface of an olefin-based resin layer, and 100 parts by weight of a polyol component; A reactive resin composition comprising a polyisocyanate component A (parts by weight) having a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) of 220 to 570 and a solvent is applied to the olefin-based resin layer and dried, and a crosslinking rate of 20 to 93 is obtained. % Urethane resin layer is formed, a second release paper is laminated on the urethane resin layer, and the reaction of the urethane resin is completed, wherein the above A is represented by the following formula. This is a method for producing the pressure-sensitive adhesive tape or sheet of the present invention. A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component)

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The first invention is a pressure-sensitive adhesive tape or sheet (hereinafter referred to as a pressure-sensitive adhesive tape or sheet) having a pressure-sensitive adhesive layer laminated on one surface of a urethane resin layer comprising a polyol component and a polyisocyanate component. "Adhesive sheet").

The polyol component has two or more hydroxyl groups in the molecule and can react with the polyisocyanate component to form a urethane resin. Any polyol conventionally used as a raw material for urethane resins can be used. There, for example, polyether polyol, polyester polyol, acrylic polyol and the like, and the adhesion of the coating film,
An acrylic polyol excellent in chemical resistance, weather resistance and the like is preferably used.

The acrylic polyol includes a copolymer of a hydroxy group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate with an alkyl (meth) acrylate. Polymers are preferred.

The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 12 or less carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate,
Examples thereof include 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate. The above may be combined and copolymerized.

If necessary, monomers such as styrene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, N-vinylpyrrolidone and the like which can be copolymerized with the above-mentioned hydroxyl group-containing (meth) acrylate and alkyl (meth) acrylate. A monomer having a polar group such as or (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, or (meth) acrylamide may be copolymerized. If necessary, two or more copolymers may be used in combination.

Glass transition temperature (Tg) of polyol component
Is lower, the resulting urethane resin becomes softer and lower in mechanical strength, and as it becomes higher, it becomes brittle.
00 ° C is preferable, and more preferably 30 to 80 ° C.

The lower the hydroxyl value of the polyol component, the lower the crosslinking density of the resulting urethane resin, the softer the mechanical strength of the resulting urethane resin becomes lower, and the higher the hydroxyl value, the higher the crosslinking density of the obtained urethane resin and the brittleness. 20-150
Is preferred.

The hydroxyl value in the present invention means the amount (mg) of potassium hydroxide necessary to neutralize acetic acid bound to acetylated product obtained from 1 g of the polyol component.
Say.

The weight average molecular weight of the polyol component is
It is not particularly limited as long as it satisfies the above Tg and hydroxyl value and can be dissolved in a solvent.
000.

The above-mentioned polyisocyanate component is a polyisocyanate having two or more isocyanate groups in a molecule and reacting with a polyol component to form a urethane resin, and a polyisocyanate having a distance between crosslinking points of 220 to 570 is used. Is done. The distance between the crosslinking points of the polyisocyanate is a value obtained by reducing the weight average molecular weight of the polyisocyanate by the number of isocyanate (NCO) groups contained in the polyisocyanate. And the value obtained by arithmetically averaging the distances between crosslinking points of each polyisocyanate by weight ratio.

When the distance between the cross-linking points of the polyisocyanate increases, the distance between the cross-linked polyols increases, and the obtained urethane resin becomes soft. When the distance decreases, the distance decreases, and the obtained urethane resin becomes hard and brittle. . Therefore, a polyisocyanate in which the distance between crosslinking points is adjusted to 220 to 570 is used.
0-550 polyisocyanates are used.

Examples of the polyisocyanate having a distance between crosslinking points of less than 220 include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5 naphthalene diisocyanate, hexamethylene diisocyanate (HDI), and isophorone diisocyanate. (IPDI), diisocyanates such as xylylene diisocyanate and tetramethyl xylene diisocyanate; trimethylolpropane adduct of diisocyanate; biuret of diisocyanate; isocyanurate of diisocyanate, and condensates thereof, and may be a mixture. . Examples of commercially available polyisocyanates having a distance between crosslinking points of less than 200 include, for example, Sumijur N3200 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.) (a solid content concentration of which is mainly 100% by weight of HDI burette, and a weight average molecular weight of 670). ,
(The number of isocyanate groups is 3.7, the distance between crosslinking points is 181 and the isocyanate group content is 23.0% by weight).

Examples of the polyisocyanate having a distance between crosslinking points of 220 to 570 include the above-mentioned diisocyanate and trimethylolpropane adduct, those obtained by adding a polyesterdiol between the isocyanate trimethylolpropane, and diisocyanate and polyesterdiol or polyester polyol. , A biuret of diisocyanate, an isocyanurate of diisocyanate, a condensate thereof or a mixture thereof.

The distance between cross-linking points actually sold is 22
Examples of the polyisocyanate of 0 to 570 include the following.

For example, Sumidur HT (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.) is HD to trimethylolpropane.
Ethyl acetate solution (solid content 75
%, Weight average molecular weight 1100, number of isocyanate groups 4.5, distance between crosslinking points 244, isocyanate group content 13.0% by weight), manufactured by Nippon Polyurethane Industry Co., Ltd.
Trade name Coronate HL is an ethyl acetate solution mainly composed of an addition of HDI to trimethylolpropane (solid content: 75% by weight, weight average molecular weight: 850, number of isocyanate groups: 3.4, distance between crosslinking points: 250, containing isocyanate groups) Coronate HLS, manufactured by Nippon Polyurethane Industry Co., Ltd., is an ethyl acetate solution (solid content: 75% by weight, weight average molecular weight: 900; The number of isocyanate groups is 2.3, the distance between crosslinking points is 391, and the isocyanate group content is 10.0% by weight.

Other examples include Desmodur E3265 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.) and Duranate E-402 (trade name, manufactured by Asahi Kasei Corporation).

Examples of the polyisocyanate having a distance between crosslinking points exceeding 570 include Desmodur TPLS2010 / 1 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.). This is a polymer of HDI (solids concentration 100
Weight%, weight average molecular weight 1540, number of isocyanate groups 2.6, distance between crosslinking points 592, isocyanate group content 10.4% by weight).

The urethane resin layer is composed of the polyol component 100
Parts by weight and polyisocyanate component A,
A is represented by the following formula. A = 100aX / Y In the formula, a is a constant and is 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the content (weight) of the isocyanate group in the polyisocyanate component. %).

The urethane resin is formed by the reaction between the hydroxyl group of the polyol component and the isocyanate group of the polyisocyanate component. If the isocyanate group is small (the addition amount of the polyisocyanate component is small), the crosslink density is low, and As the number of hydroxyl groups increases, the resulting urethane resin layer becomes soft and sticky or lacks mechanical strength. Conversely, when the number of isocyanate groups increases (the amount of the polyisocyanate component increases), the crosslink density decreases. Since the deformation following ability becomes higher and the mechanical strength tends to change with time due to excess isocyanate groups remaining, the polyisocyanate component is added in the above range, and the preferable range of a is 0.075 to 0.12
5

As the pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive,
Conventionally known arbitrary pressure-sensitive adhesives such as a rubber-based pressure-sensitive adhesive, a silicon-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive can be used, and when the pressure-sensitive adhesive sheet of the present invention is used as a marking sheet, it is often used outdoors. Therefore, an acrylic pressure-sensitive adhesive having excellent weather resistance is preferable.

The form of the pressure-sensitive adhesive is not particularly limited, and any conventionally known pressure-sensitive adhesives such as a solvent type, an emulsion type and a hot melt type can be used.

The pressure-sensitive adhesive sheet of the present invention is obtained by laminating a pressure-sensitive adhesive layer on one surface of the urethane resin layer. When the thickness of the urethane resin layer is small, it becomes soft and stiff and difficult to handle, and when it becomes thick, it becomes hard. The thickness is preferably from 30 to 120 μm, more preferably from 40 to 100 μm, since the followability to the adherend is reduced and it becomes difficult to adhere.

The thickness of the pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive sheet can be sufficiently firmly adhered to the adherend.
To 80 μm, preferably 20 to 50 μm.

Therefore, the thickness of the pressure-sensitive adhesive sheet is 40 to 200.
μm is preferred, and more preferably 60 to 150 μm.

The mechanical properties of the pressure-sensitive adhesive sheet of the present invention are 5 ° C.
And the strength at 2% elongation at 0.40 to 2.
20 kg / 15 mm width and elongation at break of 50 to 300
%.

When the pressure-sensitive adhesive sheet is applied while being stretched slightly so as to follow the adherend, if the extension strength is too weak, it is unnecessarily stretched to make it difficult to apply, and if it is too strong, it becomes difficult to stretch and it can be made to follow. It becomes difficult, and even if it can be adhered, it peels off with the lapse of time and is likely to float. Therefore, the pressure-sensitive adhesive sheet has a strength at 2% elongation of 0.40 to 2.0 at normal temperature, that is, 5 ° C and 35 ° C. 20
Kg / 15 mm width is required, and preferably 0.50 to 2.10 Kg / 15 mm width.

In the method of measuring the strength at 2% elongation in the present invention, a 15 mm-wide pressure-sensitive adhesive sheet is held at 100 mm intervals, pulled at a pulling speed of 200 mm / min, and the stress at 2% elongation is measured. .

If the elongation at break is small, the elongation at break is required to be 50 to 300%, and it is necessary to be 50 to 300%. 250%.

In the method of measuring the elongation at break in the present invention, a pressure-sensitive adhesive sheet having a width of 15 mm was held at intervals of 100 mm and pulled at a pulling speed of 200 mm / min until the pressure-sensitive adhesive sheet was broken, whereby the pressure-sensitive adhesive sheet was cut. The extended length at the time was represented by a ratio (%) to the original pressure-sensitive adhesive sheet.

Further, the residual stress of the pressure-sensitive adhesive sheet is increased by 10% because if a large amount of residual stress remains after the adhesive sheet is stretched and adhered, it is likely that floating or peeling will occur with time.
It is preferable that the residual stress ratio after 60 minutes is 60% or less.

The method for measuring the stress residual ratio in the present invention is as follows. A pressure-sensitive adhesive sheet having a width of 15 mm is held at intervals of 100 mm, pulled at a pulling speed of 200 mm / min, stretched 10%, and held as it is. Measure the residual stress of
It was expressed as a ratio (%) to the stress at 10% elongation.

The second invention is a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive sheet of the first invention, wherein an olefin resin layer is laminated between the urethane resin layer and the pressure-sensitive adhesive layer.

As the olefin resin, for example,
Polyethylene resin, polypropylene resin, ethylene-propylene copolymer, ethylene or propylene, and butene-1, pentene-1, hexene-1, heptene-
Α- such as 1, octene-1, 4-methyl-1-pentene
Any conventionally known olefin resin such as a copolymer with an olefin, an ethylene-vinyl acetate copolymer, and an ethylene-acrylic acid copolymer can be used.

When the olefin-based resin layer is laminated, the mechanical properties of the pressure-sensitive adhesive sheet are almost dominated by the mechanical properties of the olefin-based resin layer, and the mechanical properties of the pressure-sensitive adhesive sheet are as described above. The mechanical properties of the base resin layer are preferably in the following ranges.

That is, the strength at 2% elongation at 5 ° C. and 35 ° C. is preferably 0.40 to 2.10 kg / 15 mm width, and the elongation at break is preferably 100% or more. Furthermore, if a lot of residual stress remains after being stretched and affixed, floating and peeling are likely to occur over time.
The residual stress ratio after 10 minutes is preferably 60% or less.

The olefin resin for forming the olefin resin layer having the above-mentioned physical properties has a weight average molecular weight of 80,000 to 500,000 and an elution amount at 0 ° C. by the cross separation method of all the resins. 30-70% by weight, 0 ° C
A polypropylene resin having an elution amount of less than 70 ° C. or less of 5 to 30% by weight of the whole resin and an elution amount of more than 70 ° C. of 20 to 60% by weight of the whole resin (hereinafter referred to as polypropylene resin (A)) Is preferred.

The weight-average molecular weight is preferably from 80,000 to 500,000, more preferably from 200,000 to 400,000, since the smaller the weight, the lower the film strength, and the larger the weight, the lower the hardness and the lower the flexibility. or,
In the cross fractionation method, a flexible resin is eluted at a low temperature, and a hard resin is eluted at a high temperature. Therefore, a polypropylene resin in which the resin is eluted within the above range is preferable.

The cross fractionation method in the second invention is as follows. First, a polypropylene resin to be measured is dissolved in o-dichlorobenzene at 140 ° C. or a temperature at which it is completely dissolved, and after cooling at a constant rate, a thin resin layer is formed on the surface of an inert carrier prepared in advance, and a crystalline resin They are formed in the order of high molecular weight and high molecular weight. Next, elution is performed with o-dichlorobenzene while increasing the temperature continuously or stepwise from 0 ° C., the concentration of the eluted resin is detected, and the elution distribution of the resin according to the temperature is measured.

In order to adjust the strength at 2% elongation and the elongation at break of the olefin resin layer, the weight average molecular weight is 80,
000 to 500,000, and 0 according to the cross fractionation method.
0 to 20% by weight of total resin at 70 ° C
The following elution amounts to 5-30% by weight of the total resin, and 70
Polypropylene resin having an elution amount of more than 70 to 90% by weight of the total resin (hereinafter referred to as polypropylene resin (B))
) May be used in combination with the polypropylene resin (A).

The polypropylene resin (B) has a large amount of elution at 70 ° C. or more at 70 to 90% by weight of the total resin, and is harder and has higher mechanical strength than the polypropylene resin (A). When a large amount of resin is added, the strength of the olefin-based resin layer at 2% elongation increases, the elongation at break decreases, the elongation at 10% increases, and the residual stress after 10 minutes increases, so that the polypropylene-based resin (A) Is 100-30
0 to 70% by weight of polypropylene resin (B) in weight%
Is preferred.

The structure of the urethane resin layer and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the second invention and the physical properties such as the strength at 2% elongation, the elongation at break, and the residual stress ratio are the same as those of the pressure-sensitive adhesive sheet of the first invention. is there.

The pressure-sensitive adhesive sheet according to the second aspect of the present invention has a urethane resin layer laminated on one surface of the olefin resin layer and a pressure-sensitive adhesive layer laminated on the other surface, but when the thickness of the olefin resin layer is reduced. The thickness is preferably from 20 to 80 μm, more preferably from 30 to 70 μm, because it becomes difficult to handle due to lack of waist, and becomes hard when it becomes thick, and the adherence to the adherend decreases and it becomes difficult to adhere. The thickness of the urethane resin layer is preferably 5 to 50 μm, more preferably 1 to 50 μm, because it becomes soft and stiff and loses its stiffness, making it difficult to handle.
0 to 30 μm.

Accordingly, the total thickness of the olefin resin layer and the urethane resin layer is preferably 25 to 130 μm, more preferably 40 to 100 μm.

The thickness of the pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive sheet can be firmly adhered to the adherend, and is generally 10 to 80 μm, preferably 20 to 50 μm.

Therefore, the thickness of the pressure-sensitive adhesive sheet is 35 to 210
μm is preferred, and more preferably 50 to 150 μm.

The pressure-sensitive adhesive sheet of the present invention may be colored by adding a coloring agent to each layer. In particular, when the pressure-sensitive adhesive sheet is used as a marking tape or sheet (hereinafter, referred to as “marking sheet”), it is necessary to be colored, and it is preferable that a coloring agent is added to the urethane resin layer.

As the colorant, any colorant used for coloring resins, paints and the like can be used, for example, dyes such as azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, and carbonium ion dyes; Calcium carbonate, barium sulfate, zinc oxide, titanium oxide,
Inorganic pigments such as chrome yellow, cadmium yellow, nickel titanium yellow, red iron oxide, cadmium red, molybdenum orange, navy blue, ultramarine, carbon black; azo pigments, phthalocyanine pigments, metal complex pigments, triphenylmethane pigments, quinacridin pigments And organic pigments such as isoindolinone pigments. These colorants may be used alone or in combination of two or more.

The amount of the colorant to be added may be appropriately determined as necessary, but it is generally preferable to add 0.1 to 70 parts by weight based on 100 parts by weight of the urethane resin.

In each layer, if necessary, a light stabilizer,
An ultraviolet absorber, an antioxidant, an antistatic agent, an antiblocking agent and the like may be added.

Examples of the light stabilizer include poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl}.
｛(2,2,6,6-tetramethyl-4-piperidyl)
Imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl-1- (2-hydroxyethyl) -4-hydroxy-succinate
Hindered amine light stabilizers such as 2,2,6,6-tetramethylpiperidine polycondensate and bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate are exemplified. These light stabilizers were obtained from Ciba Specialty Chemicals Co., Ltd.
It is marketed under the trade names Tinuvin 622 and Tinuvin 123.

When the above-mentioned light stabilizer is added to the urethane resin layer, the so-called amine in which the hydrogen of the amine group is substituted and the nitrogen is connected to the alkyl group or the main chain, so that the amine group does not inhibit the urethane crosslinking reaction, is used. The so-called NOR type, in which hydrogen of an NR type and an amine group are substituted and nitrogen is linked to an alkyl group or a main chain via oxygen, is preferable.
22 and Tinuvin 123 are preferably used.

Examples of the ultraviolet absorbent include Tinuvin 32 (trade name, manufactured by Ciba Specialty Chemicals).
7, a benzotriazole-based ultraviolet absorber such as Tinuvin 328, a benzophenone-based ultraviolet absorber such as Chimasorpe 81 manufactured by Ciba Specialty Chemicals, and a triazine-based ultraviolet absorber such as Tinuvin 900 manufactured by Ciba Specialty Chemicals. No.

Examples of the antioxidant include Irganox 1 (trade name, manufactured by Ciba Specialty Chemicals)
010, Irganox 1076 and other hindered phenolic antioxidants, manufactured by Asahi Denka Co., Ltd., trade name ADK STAB P
And phosphorus-based antioxidants such as EP8.

Examples of the antistatic agent include surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants, and conductive powders such as carbon black. Can be

Examples of the anti-blocking agent include inorganic fine powders such as silica and alumina, glass beads,
Silicone fine particles and the like can be mentioned.

The method for producing the pressure-sensitive adhesive sheet of the first and second aspects of the present invention is not particularly limited, and it may be produced by any conventionally known method, and the third to fifth aspects of the present invention described in detail below. It is preferable that the adhesive sheet is produced by a method for producing an adhesive sheet.

A third aspect of the present invention is the method for producing a pressure-sensitive adhesive sheet according to the first aspect of the present invention, wherein a step of obtaining a first laminate in which a pressure-sensitive adhesive layer is laminated on one surface of a first release paper, 100 parts by weight of a component, a reactive resin composition comprising a polyisocyanate component A part by weight and a solvent are applied to a second release paper,
After drying, the cross-linking rate is 20 to 93% on one side of the second release paper.
Obtaining a second laminate having the urethane resin layer formed thereon, and the first laminate so that the pressure-sensitive adhesive layer of the first laminate is in contact with the urethane resin layer of the second laminate. And the second
To complete the reaction of the urethane resin.

The step of obtaining the first laminate is a step of forming an adhesive layer on one surface of the first release paper. The first
As the release paper, any release paper generally used as a release paper such as an adhesive sheet or an adhesive label can be used.For example, polyethylene paper in which polyethylene is laminated on a paper base material such as high-quality paper or kraft paper can be used. Laminated paper; high quality paper,
Clay-coated paper in which clay is laminated on a paper substrate such as kraft paper; glassine paper; super calendered paper; a silicone-based release agent on a substrate such as a plastic film such as a polyethylene terephthalate film, a stretched polypropylene film, or a polyethylene film; Release paper on which a release agent such as an alkyl pendant release agent or a fluorine release agent is laminated.

Any known method may be used for forming the pressure-sensitive adhesive layer. For example, when the pressure-sensitive adhesive is a solvent type or an emulsion type, a method of applying and drying on release paper, a method of hot melt In the case of the type, there is a method of melting and extruding on release paper and laminating.

In the step of obtaining the second laminate, the reactive resin composition is applied to a second release paper and dried, and one surface of the second release paper is coated with a urethane resin having a crosslink rate of 20 to 93%. This is a step of forming a layer.

The above-mentioned reactive resin composition contains the polyol component 1
The polyisocyanate is composed of 00 parts by weight, a polyisocyanate component A and a solvent. The polyisocyanate is obtained by blocking the isocyanate with an alcohol such as phenol or cyclohexanone oxime. Since the reaction proceeds quickly when mixed, a polyol solvent solution and a polyisocyanate solvent solution are prepared separately,
It is preferable that both are mixed to obtain a reactive resin composition, and then applied to a second release paper and dried.

As the above solvent, any solvent can be used as long as it can dissolve the polyol component and the polyisocyanate component. Examples thereof include ethyl acetate, toluene, and the like.
Xylene, butyl acetate, isobutyl acetate, methyl isobutyl ketone and the like can be mentioned. Alternatively, a mixed solvent may be used. Examples of commercially available products include Solvesso (trade name, manufactured by Exxon Chemical Co., Ltd.).

The concentration of the polyol solvent solution may be determined as appropriate. However, since the polyol component is a high molecular weight material, the higher the concentration, the higher the viscosity and the more difficult to mix and coat. Is preferred. Also, the concentration of the polyisocyanate solvent solution may be appropriately determined, but since the polyisocyanate component has a low molecular weight and a low viscosity, a high concentration is preferable so that mixing efficiency with the polyol component is good and drying efficiency is good. 50 to 10
0% by weight is preferred.

When a colorant, a light stabilizer, an ultraviolet absorber, an antioxidant, and the like are added to the urethane resin layer, it is preferable to add them to a polyol solvent solution and dissolve or disperse them.

Further, in order to adjust the reaction rate between the polyol component and the polyisocyanate component, a catalyst generally used in producing a urethane resin may be added. Examples of such a catalyst include amine catalysts such as triethylamine, triethylenediamine, and dimethylaminoethanol; tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; zinc catalysts; and lead catalysts.

The amount of the catalyst to be added may be appropriately determined as necessary, but is generally 0.05 to 1.0 with respect to 100 parts by weight of the total amount of the polyol component and the polyisocyanate component.
Parts by weight.

The reactive resin composition applied to the second release paper takes a long time to crosslink, so that the solvent is initially boiled at a low temperature below the boiling point so that the solvent does not boil and foam. It is preferable that the solvent is evaporated and the solvent is volatilized to some extent, and then heated to a temperature not lower than the boiling point to promote the progress of crosslinking and reduce the residual solvent.

Since the reaction rate of the reactive resin composition becomes slower as the reaction proceeds, the first resin is formed on one surface of the second release paper when the urethane resin layer having a crosslinking rate of 20 to 93% is formed. The first laminate and the second laminate are laminated such that the pressure-sensitive adhesive layer of the laminate and the urethane resin layer of the second laminate are in contact with each other, and the first release paper, the pressure-sensitive adhesive layer, the urethane resin A four-layer laminate in which the layer and the second release paper are laminated is obtained, and then the reaction of the urethane resin is completed. To complete the reaction of the urethane resin, curing may be performed at 10 to 60 ° C. for 1 to 10 days.

Incidentally, the above-mentioned cross-linking ratio means that the urethane resin is supplied to a shaker, swelled and dissolved in ethyl acetate at 23 ° C. for 24 hours, and then filtered through a 200-mesh wire net. It refers to the ratio (% by weight) to the resin.

As described above, since the reaction rate of the reactive resin composition becomes slower as the reaction proceeds, it is necessary to continuously complete the reaction of the reactive resin composition during the manufacturing process.
A large amount of heat and time are required, and the productivity is low. However, by performing the above-described steps, it is possible to manufacture the product with high productivity.

The second release paper is not particularly limited, and the release paper described in detail as the first release paper can be used.
Also, since the physical adhesion of the urethane resin (reactive resin composition) is lower than that of the pressure-sensitive adhesive, the urethane resin layer (reactive resin composition) has no reactivity with the isocyanate group of the urethane resin layer (reactive resin composition), and has a low polarity. For example, polypropylene film,
Plastic films such as polyethylene terephthalate films and polyethylene films and stretched films thereof can also be used.

The second release paper is a so-called process paper.
The pressure-sensitive adhesive sheet after curing is used before or after application to an adherend, and is used.
When the adhesion between the urethane resin layer and the second release paper is reduced during the transportation or winding of the four-layer laminate and during the storage and storage and the secondary processing for commercialization, the adhesion between the urethane resin layer and the second release paper is reduced. And the appearance of the urethane resin layer becomes poor. Conversely, when the size is large, it becomes difficult to peel off the second release paper, the second release paper breaks, or the peeling is intermittent, so that the urethane resin layer has a step mark and poor appearance occurs. Become.

Accordingly, it is preferable that the second release paper has a 180-degree peel strength of 5 to 200 g / 50 mm width measured at a peel speed of 300 mm / min after the completion of the urethane resin reaction. In addition, "after completion of the reaction of the urethane resin" means immediately after curing at 40 ° C. for 24 hours after obtaining a four-layer laminate.

The urethane resin layer becomes a surface layer when the obtained pressure-sensitive adhesive sheet is adhered to an adherend. In particular, when the urethane resin layer is used as a marking sheet, design properties may be required. In the above manufacturing method, the urethane resin is applied to the second release paper as a reactive resin composition and dried, and after the reaction of the urethane resin is completed, the second release paper is peeled off. The surface shape of the release paper is transferred. Therefore, when it is required that the surface of the urethane resin layer is smooth, it is preferable to use a smooth release paper, and when it is required that the surface of the urethane resin layer is matted, It is preferable to use release paper whose surface has been subjected to unevenness processing by processing such as roll processing, sand blast processing, or the like.

A fourth aspect of the present invention is the method for producing a pressure-sensitive adhesive sheet according to the second aspect of the present invention, wherein a pressure-sensitive adhesive layer and a first release paper are sequentially laminated on one surface of an olefin-based resin layer. Step of obtaining a body, 100 parts by weight of a polyol component, A part by weight of a polyisocyanate component, and a reactive resin composition comprising a solvent are applied to a second release paper, and dried. A step of obtaining a second laminate in which a urethane resin layer of 20 to 93% is formed, and a step of contacting the olefin-based resin layer of the first laminate with the urethane resin layer of the second laminate. It comprises a step of laminating the first laminate and the second laminate to complete the reaction of the urethane resin.

The step of obtaining the first laminate is a step of sequentially laminating the pressure-sensitive adhesive layer and the first release paper on one surface of the olefin-based resin layer. The method for forming each layer is not particularly limited,
Any method may be adopted, for example, (1) a method of co-extruding an olefin-based resin and a hot-melt type pressure-sensitive adhesive and laminating a first release paper on the pressure-sensitive adhesive layer, and (2) a third present invention. As described in detail above, a method in which an adhesive layer is formed on the first release paper, and then a separately formed olefin resin film is laminated, (3) First, an olefin resin film is prepared and There is a method of laminating an adhesive layer, and laminating a first release paper thereon.

The step of obtaining the second laminate is the same as the step of obtaining the second laminate in the third invention. Then
The third present invention has been described in detail except that the first laminate and the second laminate are laminated so that the olefin-based resin layer of the first laminate and the urethane resin layer of the second laminate are in contact with each other. Thus, the reaction of the urethane resin is completed.

A fifth aspect of the present invention is the method for producing a pressure-sensitive adhesive sheet according to the second aspect of the present invention, wherein a pressure-sensitive adhesive layer and a first release paper are sequentially laminated on one surface of an olefin-based resin layer. A step of obtaining a body, and applying a reactive resin composition comprising 100 parts by weight of a polyol component, A parts by weight of a polyisocyanate component and a solvent to the olefin-based resin layer and drying the urethane resin to have a crosslinking ratio of 20 to 93%. After forming the layer, a step of laminating a second release paper on the urethane resin layer to complete the reaction of the urethane resin is included.

The step of obtaining the first laminate is the same as the step of obtaining the first laminate in the fourth invention.

Next, in the fifth aspect of the present invention, a reactive resin composition comprising 100 parts by weight of a polyol component, A part by weight of a polyisocyanate component and a solvent is applied on the olefin-based resin layer, and dried to obtain a crosslink rate of 20%. A ~ 93% urethane resin layer is formed. This forming method is the same as that of the second embodiment except that the first laminate is used in place of the release paper.
This is the same as the step of obtaining the laminate.

Finally, a second release paper is laminated on the urethane resin layer cross-linked at a cross-linking rate of 20 to 93% to complete the reaction of the urethane resin. The second release paper is laminated on the urethane resin layer of the four-layer laminate in which the first release paper, the adhesive layer, the olefin-based resin layer, and the urethane resin layer are sequentially laminated.
It is easily performed by overlapping and pressing the release paper, but it is preferable to perform the overlapping and pressing at a temperature near the glass transition temperature of the urethane resin. The method of completing the reaction of the urethane resin is as detailed in the third invention.

In the present invention, in order to improve the adhesiveness between the pressure-sensitive adhesive layer and the urethane resin layer or the olefin resin layer and the adhesion between the urethane resin layer and the olefin resin layer, the urethane resin layer and the olefin resin layer are used. One or both of the layers may be subjected to a surface polarity imparting treatment such as a corona discharge treatment or a flame treatment, or may be laminated with a primer commonly used as a primer for an adhesive tape.

[0095] Any laminating method such as a method of laminating the first laminate and the second laminate and a method of laminating the second release paper on the urethane resin layer may be adopted. For example, a method in which both layers are superposed and then pressed, a method in which both layers are superposed and then pressed while being heated by a heating roll, and the like can be used.

[0096]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

First, the materials used in the examples will be described. In the examples, acrylic polyol, polyisocyanate, olefin-based resin and release paper are represented by the following abbreviations.

Acrylic polyols Acrylic polyols A1, A2, A4 and A5 are listed in Table 1.
2 is a solution of a predetermined amount of a copolymer of monomers in ethyl acetate. The copolymer concentration was 40% by weight, and the glass transition temperature Tg and hydroxyl value are shown in Table 1.

The acrylic polyol A3 is a copolymer composed of 16% by weight of 2-hydroxyethyl methacrylate, 10% by weight of isobutyl methacrylate, 8% by weight of 2-ethylhexyl acrylate, 50% by weight of methyl methacrylate, 15% by weight of styrene and 1% by weight of methacrylic acid. 100 parts by weight of a polymer (having a hydroxyl value of 70 mg / g) in ethyl acetate (copolymer concentration is 40% by weight) and an ethyl acetate solution of a caprolactone-modified polyester diol (having a hydroxyl value of 45 mg / g and a weight average molecular weight of about 2000) (Japan (Paint Co., Ltd., trade name: Softener 5, diol concentration: 75% by weight)
It is a mixture consisting of 8 parts by weight.

The glass transition temperature Tg and the hydroxyl value are shown in Table 1.

[0101]

[Table 1]

[0102] using a mixture of a polyisocyanate and a predetermined amount of polyisocyanate indicated in polyisocyanate Table 2. Table 2 shows the distance between crosslinking points.

[0103]

[Table 2] HLS: manufactured by Nippon Polyurethane Co., trade name Coronate HL
SHL: manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate HL N3200; manufactured by Sumitomo Bayer Urethane Co., Ltd .; trade name: Sumijur N3200 TPLS; manufactured by Sumitomo Bayer Urethane Co., trade name: Desmodur TPLS2010 / 1

[0104] Elution amount of the cross fractionation method of the olefin resin used to form the olefin-based resin olefinic resin layer and the weight average molecular weight are shown in Table 3.

[0105]

[Table 3] KS: polypropylene resin, manufactured by Montelus d'Sunrise Co., Ltd., trade name Adflex KS081P M40; linear low-density polyethylene, manufactured by Tosoh Corporation, trade name: Nipolon L-M40 PP: polypropylene resin, manufactured by Nippon Polyolefin Co., trade name: J Allomer PC630S EBR; ethylene butene copolymer, manufactured by Sumitomo Chemical Co., Ltd.
Product name Espleno NO416

Adhesive n-butyl acrylate 70.0% by weight, 2-ethylhexyl acrylate 20.0% by weight, acrylic acid 9.7
% By weight and 0.3% by weight of 2-hydroxyethyl acrylate (weight average molecular weight 60
100 parts by weight of a 30% by weight ethyl acetate solution having a weight average molecular weight / number average molecular weight of 4.5) was mixed with an isocyanate-based crosslinking agent (Coronate L-, trade name, manufactured by Nippon Polyurethane Co., Ltd.).
1.0 part by weight of 55E, a 55% solids concentration ethyl acetate solution) were mixed and used as an adhesive.

Colorant Chromophtal DPP Red BP, trade name, manufactured by Ciba Specialty Chemicals

Release paper C1; double-sided polyethylene laminated paper having one side subjected to silicone release treatment, manufactured by Kite Chemical Industry Co., Ltd., trade name Smiley SLK-110
AW C2: Stretched polypropylene film, manufactured by Nimura Chemical Co., Ltd., trade name: Taiko FOA-P2 C3; Paper treated on both sides with alkyd resin, manufactured by Lintec Co., Ltd., trade name: Kouteishi ES160 C4; , Trade name Taiko FOR-MP2 C5; polyethylene terephthalate film treated on both sides with alkyd resin manufactured by Teijin Ltd., trade name Tetron film S-PZ C6; polyethylene terephthalate film treated on both sides with silicone release treatment, manufactured by Teijin Ltd., trade name view Rex

Next, a method for measuring physical properties and the like will be described. In addition, the hydroxyl value of the polyol component, the crosslinking ratio of the urethane resin, 2%
The methods for measuring the strength at elongation, the elongation at break, the residual stress ratio, the cross fractionation, and the 180-degree peel strength between the urethane resin layer and the second release paper are as described in the detailed disclosure section of the invention.

[0110] supplying an adhesive sheet obtained curable to 110 ° C. hot air oven, dried for 5 minutes, pressing the gauze urethane resin layer was observed adhesion state on the gauze. ○: no gauze adhered ×: gauze adhered

Gauze was pressed against the urethane resin layer of the obtained pressure-sensitive adhesive sheet so that the load became 10 g / cm ² , left at 40 ° C. for 24 hours, the gauze was removed, and the surface of the urethane resin layer was observed. ；: No significant change in surface gloss was observed. Δ: A slight change was observed in surface gloss. ×: A large change was observed in surface gloss.

Cut property The obtained pressure-sensitive adhesive sheet was supplied to a cutting machine manufactured by Mimaki Engineering Co., Ltd., and characters of 10 mm size were cut, and the cut state was observed. ○: Completely cut △: Partially turned up ×: Partially not cut, character torn during scrap removal

[0113] bondability radius of curvature 20 mm, between the top portion of the aluminum corrugated plate depth 15 mm, after stretched the resulting adhesive sheet, paste pressed while extending an adhesive sheet in the valley portion, 23 ° C. After one week, the peeling (floating) state of the adhesive sheet was observed. ；: Floating with a width of 1 mm or less occurred. ；: Floating occurred around the bottom. ×: Floating occurred on the entire surface, and the adhesive sheet did not follow during attachment and was broken.

Workability An adhesive sheet of 100 mm square was adhered to an aluminum plate, and the adhered state was observed. ○: those that could be pasted without wrinkles △; those that were easily wrinkled and difficult to paste ×; those that had wrinkles

[0115] The weather resistance obtained pressure-sensitive adhesive sheet was supplied to the sunshine weather meter, and observation of the surface state after 2000 hours of exposure. ；: Almost no change △: slight discoloration, difference in glossiness ×: apparently different appearance

Combustion chlorine generation test The obtained pressure-sensitive adhesive sheet was burned in a closed container, the generated gas was captured in water, and chlorine was measured by gas chromatography (detection limit: 20 ppm). ; Those that can detect chlorine

Adhesion The obtained adhesive sheet was supplied to a sunshine weather meter, and after exposure for 1000 hours, a 10 mm square adhesive sheet was cut at every 1 mm in accordance with JIS-K5400 cross cut evaluation method, and 100 pieces were cut. Form squares,
The cellophane tape was peeled off after pressure bonding, and the squares where the urethane resin layer was peeled off were counted. ○: No peeling △: 1 to 25 peeled squares ×: 26 or more peeled squares

Examples 1 to 6 and Comparative Examples 1 to 6 The adhesive was applied to the first release paper C1 with a baker-type applicator and dried in a hot-air oven at 110 ° C. for 5 minutes to form an adhesive layer having a thickness of 30 μm. The obtained first laminate was obtained.

A predetermined amount (solid content) of an acrylic polyol, a polyisocyanate, a colorant and a catalyst (dioctyltin dilaurate, trade name: Stan SNT-1F, manufactured by Sankyoki Gosei Co., Ltd.) shown in Tables 4 and 5 are 0.1. A mixture obtained by mixing 1 part by weight of a light stabilizer and 1 part by weight of a light stabilizer (trade name: Tinuvin 622, manufactured by Ciba Specialty Chemicals) was applied to a second release paper C2 with a baker-type applicator, and then applied to a second release paper C2.
The resultant was dried in a hot-air oven at 5 ° C. for 5 minutes to obtain a second laminate on which a urethane resin layer having a predetermined thickness shown in Tables 4 and 5 was formed.

The pressure-sensitive adhesive layer of the obtained first laminate was
Laminated so that the urethane resin layer of the laminate of
The pressure-sensitive adhesive sheet was laminated by pressing with a heating roll at a temperature of 100 ° C. The obtained pressure-sensitive adhesive sheet is
After curing at 3 ° C. for 3 days, the physical properties of the pressure-sensitive adhesive sheet were measured, and the results are shown in Tables 4 and 5.

Further, the crosslinking rate of the urethane resin at the time of lamination and the 180-degree peel strength of the second release paper C2 were measured.
The results are shown in Tables 4 and 5.

Comparative Example 7 Vinyl chloride resin (manufactured by Kanegafuchi Chemical Industry Co., Ltd., trade name: PHS-1)
0) 100 parts by weight, colorant 7 parts by weight, adipate ester plasticizer (Adekaizer P, manufactured by Asahi Denka Kogyo KK)
N300) 30 parts by weight, 5 parts by weight of barium / zinc composite heat stabilizer (manufactured by Asahi Denka Kogyo KK, trade name: MARK SC34) and 150 parts by weight of a mixed solvent (manufactured by Exxon Chemical Company, trade name: Solvesso) are obtained. Release sol into release paper C3
Was applied with a baker-type applicator so that the coating thickness after drying was 50 μm, and dried in a hot air oven at 200 ° C. for 8 minutes to obtain a 50 μm thick vinyl chloride resin film.

The first laminate obtained in Example 1 was superimposed on the obtained vinyl chloride resin film so that the pressure-sensitive adhesive layer was in contact therewith, and was laminated by pressing with a heating roll at a temperature of 100 ° C. I got a sheet. After curing the obtained pressure-sensitive adhesive sheet at 40 ° C. for 3 days, the physical properties of the pressure-sensitive adhesive sheet were measured, and the results are shown in Table 5.

[0124]

[Table 4]

[0125]

[Table 5]

Examples 7 to 12, Comparative Example 8 100 parts by weight of the olefin resin shown in Tables 6 and 7, 3.5 parts by weight of titanium oxide powder, an antioxidant (trade name: Irganox, manufactured by Ciba Specialty Chemicals) 107
6) 0.007 parts by weight and 0.021 of a light stabilizer (trade name: Tinuvin 622, manufactured by Ciba Specialty Chemicals)
The compound consisting of parts by weight was supplied to an extruder and extruded with a T-die at 230 ° C. (200 ° C. in Example 7 only) to obtain an olefin resin film having a predetermined thickness shown in Tables 6 and 7. The physical properties of the obtained olefin resin film were measured, and the results are shown in Tables 6 and 7.

Both surfaces of the obtained film were subjected to a corona discharge treatment, and the surface energy of the film was adjusted to 45 dynes by the measured value of the wetting reagent.

The pressure-sensitive adhesive was applied to the first release paper C1 with a baker-type applicator and dried in a hot-air oven at 110 ° C. for 5 minutes to form a pressure-sensitive adhesive layer having a thickness of 30 μm. Superimposed on the first
Was obtained.

A predetermined amount (solid content) of an acrylic polyol, a polyisocyanate, a colorant, and a catalyst (dioctyltin dilaurate, trade name Stan SNT-1F manufactured by Sankyoki Gosei Co., Ltd.) 0.1 shown in Tables 6 and 7 A mixture of 1 part by weight of a light stabilizer and 1 part by weight of a light stabilizer (trade name: Tinuvin 622, manufactured by Ciba Specialty Chemicals) was applied to the olefin resin film surface of the first laminate with a baker-type applicator, and heated at 110 ° C. with hot air. After drying in an oven for 5 minutes, a urethane resin layer having a predetermined thickness shown in Tables 6 and 7 was formed, and then release paper C2 was laminated on the urethane resin layer to obtain an adhesive sheet. The obtained pressure-sensitive adhesive sheet was heated at 40 ° C.
After curing for 3 days, the physical properties of the pressure-sensitive adhesive sheet were measured, and the results are shown in Tables 6 and 7.

Further, the cross-linking ratio of the urethane resin and the 180-degree peel strength of the release paper C2 when laminating the release paper C2 were measured. The results are shown in Tables 6 and 7.

Comparative Example 9 Vinyl chloride resin (manufactured by Kanegafuchi Chemical Co., Ltd., trade name: PHS-1)
0) 100 parts by weight, 30 parts by weight of titanium oxide powder (manufactured by Dainichi Seika Industry Co., Ltd., trade name: DAP050 white), adipic acid ester plasticizer (manufactured by Asahi Denka Kogyo Co., Ltd.)
30 parts by weight of Adekasizer PN300 (trade name), barium / zinc composite heat stabilizer (manufactured by Asahi Denka Kogyo KK, trade name MA)
RK SC34) 5 parts by weight and a sol obtained by mixing 150 parts by weight of a mixed solvent (manufactured by Nippon Mining Co., Ltd., trade name: Solvesso) on a release paper C3 so that the coating film thickness after drying becomes 50 μm. Apply with a formula applicator, 20
It was dried in a hot air oven at 0 ° C. for 8 minutes to obtain a vinyl chloride resin film having a thickness of 40 μm. The physical properties of the obtained vinyl chloride resin film were measured, and the results are shown in Table 7 in the column of physical properties of the olefin-based resin layer.

Both surfaces of the obtained film were subjected to corona discharge treatment, and the surface energy of the film was adjusted to 45 dynes as measured by a wetting reagent.

An adhesive was applied to the first release paper C1 with a baker-type applicator, and dried in a hot-air oven at 110 ° C. for 5 minutes to form an adhesive layer having a thickness of 30 μm. First film
Was obtained.

A predetermined amount (solid content) of an acrylic polyol, a polyisocyanate, a colorant, and a catalyst (dioctyltin dilaurate, manufactured by Sankyoki Gosei Co., Ltd., trade name: Stan SNT-1F) in an amount of 0.1 part by weight shown in Table 7 and A mixture obtained by mixing 1 part by weight of a light stabilizer (trade name: Tinuvin 622, manufactured by Ciba Specialty Chemicals) is applied to the vinyl chloride resin film surface of the first laminate with a baker-type applicator, and then heated in a 110 ° C. hot air oven. After drying for 5 minutes, a urethane resin layer having a thickness of 20 μm was formed, and then release paper C2 was laminated on the urethane resin layer to obtain an adhesive sheet. After curing the obtained adhesive sheet at 40 ° C. for 3 days,
The physical properties of the pressure-sensitive adhesive sheet were measured, and the results are shown in Table 7.

Further, the cross-linking rate of the urethane resin when laminating the release paper C2 and the 180 ° peel strength of the release paper C2 were measured. The results are shown in Table 7.

Comparative Example 10 100 parts by weight of the olefin resin shown in Table 7 and 3.5 parts by weight of titanium oxide powder, an antioxidant (trade name: Irganox 1076, manufactured by Ciba Specialty Chemicals)
A mixture of 007 parts by weight and 0.021 parts by weight of a light stabilizer (trade name: Tinuvin 622, manufactured by Ciba Specialty Chemicals Co., Ltd.) was supplied to an extruder, and extruded at 230 ° C. with a T-die to obtain a 50 μm thick olefin resin film. I got The physical properties of the obtained olefin resin film were measured, and the results are shown in Table 7.

One surface of the obtained film was subjected to a corona discharge treatment, and the surface energy of the film was adjusted to 45 dynes by the measured value of the wetting reagent.

The adhesive was applied to the first release paper C1 with a baker-type applicator and dried in a hot-air oven at 110 ° C. for 5 minutes to form an adhesive layer having a thickness of 30 μm. Were subjected to corona discharge treatment to obtain an adhesive sheet. The physical properties of the obtained pressure-sensitive adhesive sheet were measured, and the results are shown in Table 7.

[0139]

[Table 6]

[0140]

[Table 7]

Examples 13 to 15 and Comparative Examples 11 and 12 The adhesive was applied to the first release paper C in the same manner as in Example 1.
1 and dried to obtain a first laminate.

The urethane resin composition used in Example 3 was applied to the second release paper shown in Table 8 so that the thickness of the urethane resin layer was 50 μm, and the furnace length was 35 m and the furnace temperature was 100 μm. The resultant was supplied to a drying oven at a feed rate shown in Table 8 and dried to obtain a second laminate.

The pressure-sensitive adhesive layer of the obtained first laminate was
Laminated so that the urethane resin layer of the laminate of
The pressure-sensitive adhesive sheet was laminated by pressing with a heating roll at a temperature of 100 ° C. The adhesion between the urethane resin layer of the obtained pressure-sensitive adhesive sheet and the second release paper was observed, and the results are shown in Table 8. After the obtained pressure-sensitive adhesive sheet was cured at 40 ° C. for 3 days, the curability of the pressure-sensitive adhesive sheet was measured.
It was shown to.

Further, the crosslinking ratio of the urethane resin during lamination and the 180 ° peel strength of the second release paper C2 were measured. The results are shown in Table 8. When the second release paper of the pressure-sensitive adhesive sheet obtained in Example 15 was peeled off, the mat shape of the second release paper was clearly transferred to the urethane resin layer.

[0145]

[Table 8]

Example 16 A first laminate was obtained in the same manner as in Example 9. On the other hand, the composition for urethane resin used in Example 9 was applied to the second release paper C2 so that the thickness of the urethane resin layer was 20 μm, and the drying furnace having a furnace length of 35 m and a furnace temperature of 100 ° C. was applied. At a feed speed of 20 m / min and dried to obtain a second laminate.

The obtained olefin-based resin layer of the first laminate and the urethane resin layer of the second laminate are laminated so as to be in contact with each other, and are laminated by pressing with a heating roll at a temperature of 100 ° C. I got The adhesion between the urethane resin layer of the obtained pressure-sensitive adhesive sheet and the second release paper was observed, and the results are shown in Table 9. Moreover, the obtained adhesive sheet is 40
After curing at 3 ° C. for 3 days, the curability and adhesion of the pressure-sensitive adhesive sheet were measured, and the results are shown in Table 9.

Further, the cross-linking rate of the urethane resin upon lamination and the 180 ° peel strength of the second release paper C2 were measured. The results are shown in Table 9.

Examples 17 to 20, Comparative Examples 13 and 14 A first laminate was obtained in the same manner as in Example 9. Next, the formulation for the urethane resin used in Example 9 was
In the same manner as in Example 9, the urethane resin layer was coated on the olefin-based resin layer of the first laminate so that the thickness of the urethane resin layer was 20 μm, and the furnace was 35 m in length and dried in a furnace at a temperature of 100 ° C. Then, the mixture was supplied at a predetermined feed speed shown in Table 9 and dried to obtain a second laminate.

A predetermined second release paper shown in Table 9 was overlaid on the urethane resin layer of the obtained second laminate,
The adhesive sheet was obtained by laminating by pressing with a heating roll at 00 ° C. The temperature of the heating roll of Example 20 was room temperature.

The adhesion between the urethane resin layer of the obtained pressure-sensitive adhesive sheet and the second release paper was observed, and the results are shown in Table 9.
After curing the obtained adhesive sheet at 40 ° C. for 3 days,
The curability and adhesion of the pressure-sensitive adhesive sheet were measured, and the results are shown in Table 9.

Further, the cross-linking rate of the urethane resin during lamination and the 180-degree peel strength of the second release paper were measured, and the results are shown in Table 9.

[0153]

[Table 9]

[0154]

Since the constitution of the pressure-sensitive adhesive tape or sheet of the present invention is as described above, the pressure-sensitive adhesive tape or sheet is flexible, has excellent ability to follow irregularities and curved surfaces of an adherend, and has excellent cutability. Further, since it does not contain chlorine, no dioxin is generated even if it is incinerated, and there is no environmental health problem. Therefore, it can be suitably used especially as a marking tape or sheet.

Since the method for producing the pressure-sensitive adhesive tape or sheet of the present invention is as described above, the pressure-sensitive adhesive tape or sheet can be easily produced.

Claims (24)

[Claims] 1. 100 parts by weight of a polyol component and a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) of 22
A pressure-sensitive adhesive tape or sheet in which a pressure-sensitive adhesive layer is laminated on one side of a urethane resin layer comprising 0 to 570 parts by weight of a polyisocyanate component A, wherein A is represented by the following formula: A = 100aX / Y (Formula Wherein a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of isocyanate group in the polyisocyanate component. 0.40
2.20 kg / 15 mm width and elongation at break of 50 to 3
A pressure-sensitive adhesive tape or sheet characterized by being 00%. 2. The polyol component has a glass transition temperature (T
The pressure-sensitive adhesive tape or sheet according to claim 1, wherein g) is an acrylic polyol having 0 to 100 ° C and a hydroxyl value of 20 to 150. 3. The urethane resin layer contains a colorant in an amount of 0.1 to 70.
The pressure-sensitive adhesive tape or sheet according to claim 1, which is added by part by weight. 4. The pressure-sensitive adhesive tape or sheet according to claim 1, wherein the distance between crosslinking points is from 250 to 550. 5. The urethane resin layer has a thickness of 30 to 120 μm.
The pressure-sensitive adhesive tape or sheet according to claim 1, which is m. 6. The pressure-sensitive adhesive tape or sheet according to claim 1, wherein the adhesive tape or sheet has 10% elongation at 23 ° C. and a residual stress after 10 minutes of 60% or less. 7. The method according to claim 1, wherein the strength at 2% elongation at 5 ° C. and 35 ° C. is 0.50 to 2.10 Kg / 15 mm width, and the elongation at break is 70 to 250%.
The pressure-sensitive adhesive tape or sheet as described in the above. 8. A marking tape or sheet comprising the pressure-sensitive adhesive tape or sheet according to claim 1. 9. A polyol component having 100 parts by weight and a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) of 22.
A pressure-sensitive adhesive tape or sheet comprising a urethane resin layer composed of 0 to 570 parts by weight of a polyisocyanate component A, an olefin-based resin layer, and a pressure-sensitive adhesive layer, which are sequentially laminated.
Is represented by the following formula: A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component. ) The strength at 2% elongation at 5 ° C. and 35 ° C. is 0.40 to 0.40.
2.20 kg / 15 mm width and elongation at break of 50 to 3
A pressure-sensitive adhesive tape or sheet characterized by being 00%. 10. The pressure-sensitive adhesive tape or sheet according to claim 9, wherein the polyol component is an acrylic polyol having a glass transition temperature (Tg) of 0 to 100 ° C. and a hydroxyl value of 20 to 150. 11. The urethane resin layer contains a colorant in an amount of 0.1 to 7
The pressure-sensitive adhesive tape or sheet according to claim 9, wherein 0 parts by weight are added. 12. The pressure-sensitive adhesive tape or sheet according to claim 9, wherein the distance between crosslinking points is from 250 to 550. 13. An olefin resin having a weight average molecular weight of 80,000 to 500,000, and an elution amount at 0 ° C. by a cross separation method of 30 to 70% by weight of the total resin amount.
The amount eluted above 0 ° C and 70 ° C or lower is 5 to 30% by weight of the total resin amount, and the amount eluted above 70 ° C is 20 to 60% of the total resin amount.
100 to 30% by weight of polypropylene resin
The weight average molecular weight is 80,000 to 500,000, the elution amount at 0 ° C. by the cross fractionation method is 0 to 20% by weight of the total resin amount, and the elution amount at 0 ° C. to 70 ° C. 5 to 30% by weight based on the total amount of the resin and 70 to 90% by weight of the total resin,
The pressure-sensitive adhesive tape or sheet according to claim 9, which comprises about 70% by weight. 14. The olefin resin layer has a strength at 23 ° C. at 2% elongation of 0.40 to 2.10 kg / 15 m.
The pressure-sensitive adhesive tape or sheet according to claim 13, wherein the m width and the elongation at break are 50% or more and 10% elongation, and the residual stress rate after 10 minutes is 60% or less. 15. The pressure-sensitive adhesive tape or sheet according to claim 9, wherein the pressure-sensitive adhesive tape or sheet has an elongation of 10% at 23 ° C. and a residual stress after 10 minutes of 60% or less. 16. The elongation at 5 ° C. and 35 ° C. at 2% elongation of 0.50 to 2.10 kg / 15 mm width and elongation at break of 70 to 250%. Adhesive tape or sheet. 17. The urethane resin layer has a thickness of 5 to 50 μm.
The pressure-sensitive adhesive tape or sheet according to claim 9, wherein the thickness of the olefin-based resin layer is 20 to 80 µm, and the total thickness of the urethane resin layer and the olefin-based resin layer is 25 to 130 µm. 18. A marking tape or sheet comprising the pressure-sensitive adhesive tape or sheet according to claim 9. 19. A step of obtaining a first laminate in which an adhesive layer is laminated on one surface of a first release paper, 100 parts by weight of a polyol component, and a distance between crosslinking points (weight average molecular weight / number of isocyanate groups) is 220. To 570 of a polyisocyanate component A and a solvent.
Coating and drying on a release paper to obtain a second laminate in which a urethane resin layer having a crosslinkage of 20 to 93% is formed on one surface of the second release paper, and a first laminate And laminating the first laminate and the second laminate so that the urethane resin layer of the second laminate contacts the urethane resin layer of the second laminate to complete the reaction of the urethane resin. The method for producing a pressure-sensitive adhesive tape or sheet according to claim 1, wherein the method is represented by the following formula: A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component) 20. The 180-degree peel strength (300 mm / min) of the second release paper after the reaction of the urethane resin is completed is 5 to 20.
The method for producing a pressure-sensitive adhesive tape or sheet according to claim 19, which has a width of 0 g / 50 mm. 21. A step of obtaining a first laminate in which an adhesive layer and a first release paper are sequentially laminated on one surface of an olefin-based resin layer, 100 parts by weight of a polyol component, a distance between crosslinking points (weight average). (A molecular weight / number of isocyanate groups) A reactive resin composition comprising a polyisocyanate component (A) having a weight of 220 to 570 and a solvent is applied to a second release paper, and dried. A step of obtaining a second laminate in which a urethane resin layer of about 93% is formed, and a step of forming a second laminate so that the olefin-based resin layer of the first laminate is in contact with the urethane resin layer of the second laminate. 10. The method of claim 9, wherein the step of laminating the first laminate and the second laminate to complete the reaction of the urethane resin is performed, wherein A is represented by the following formula. Method. A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component) 22. The 180 ° peel strength (300 mm / min) of the second release paper after completion of the reaction of the urethane resin is 5 to 20.
The method for producing a pressure-sensitive adhesive tape or sheet according to claim 21, which has a width of 0 g / 50 mm. 23. A step of obtaining a first laminate in which an adhesive layer and a first release paper are sequentially laminated on one surface of an olefin-based resin layer, 100 parts by weight of a polyol component, and a distance between crosslinking points ( A weight average molecular weight / number of isocyanate groups) of a reactive resin composition comprising a polyisocyanate component A having a weight ratio of 220 to 570 and a solvent is applied to the olefin resin layer and dried, and a urethane resin layer having a crosslinking ratio of 20 to 93%. And forming a second release paper on the urethane resin layer to complete the reaction of the urethane resin, wherein A is represented by the following formula. A method for producing a tape or sheet. A = 100aX / Y (where a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, and Y is the weight% of the isocyanate group in the polyisocyanate component) 24. The 180 ° peel strength (300 mm / min) of the second release paper after the reaction of the urethane resin is completed is 5 to 20.
The method for producing a pressure-sensitive adhesive tape or sheet according to claim 23, which has a width of 0 g / 50 mm.