JP2005097632A - Marking tape or sheet, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a marking tape or sheet which is flexible, has excellent following capability to an object to be stuck, is easy to cut and is excellent in coloring properties, weather resistance and so on, and its manufacturing method. <P>SOLUTION: The marking tape or sheet is prepared by laminating a pressure-sensitive adhesive layer on the surface of a urethane resin layer which is prepared by reacting and curing 100 pts.wt. polyol component and A pts.wt. polyisocyanate component having a distance between cross-linking points (weight-average molecular weight/number of isocyanate groups) of 220-570. The above A is expressed by a following formula: A=100aX/Y (wherein, a is a constant; 0.067 to 0.135, X is a hydroxyl value of the polyol component, and Y is percent by weight of isocyanate groups in the polyisocyanate component). The marking tape or sheet has a strength at 2% elongation of 0.40 to 2.20 kg/15 mm width and has a breaking elongation of 50-300% at 5°C and 35°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a marking tape or sheet excellent in flexibility, followability to an adherend, cut property, colorability, and the like, and a method for producing the same.

The so-called vinyl tape, which is made of soft vinyl chloride resin as a base material and laminated with an adhesive layer on one side, is excellent in flexibility, followability to adherends, cutability, electrical insulation, etc. Since it is easy to color and impart weather resistance, it is widely used in applications such as electrical insulating tapes, anticorrosion tapes, sealing tapes, and marking sheets.

Among these, the marking sheet is used for, for example, advertising stickers used for signs, advertising boards, shutters, windows, etc .; decorative stripe stickers used for automobiles, motorcycles, motor boats, snowmobiles, etc .; used for traffic signs, information boards, etc. Although widely used for display stickers, etc., it is required to follow the unevenness and curved surface of the adherend and not shrink with time, so the base material is made of vinyl chloride resin with plasticizer, pigment, etc. In general, the calendering method is used, and in particular, a marking sheet that requires high quality in terms of weather resistance and strength is formed by the casting method (for example, Patent Document 1).

However, since vinyl chloride resin contains chlorine, dioxins are generated when it is incinerated after use, so there is a problem in terms of environmental hygiene, and it has the same properties as vinyl tape based on a resin that does not contain chlorine. An adhesive tape or sheet is desired.

For example, Patent Document 2 describes a marking film using a polyurethane film as a base material, and the polyurethane film has isocyanate components such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate as isocyanate components. Since diisocyanate having a short distance between the groups is used, the flexibility is insufficient, and the adherence to the unevenness and curved surface of the adherend is insufficient.

In Patent Document 3, the weight average molecular weight is 80,000 to 500,000, and the amount of elution 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 more than 10 ° C. Elution amount at 70 ° C or less is 5 to 35% by weight of the total resin amount, elution amount at 70 ° C or more and 95 ° C or less is 1 to 30% by weight of the total resin amount, and elution amount at 95 ° C or more and 125 ° C or less Describes a marking film using as a base material a polypropylene-based resin having 3 to 35% by weight of the total resin amount. This polypropylene resin is too soft, and a glossy film cannot be obtained, and the obtained film has a drawback that it is difficult to cut. In addition, the weather resistance is low, and even if a stabilizer is added, it can be used only for about two years.

Japanese Patent Publication No. 5-88862 JP-A-3-45672 JP-A-8-20750

An object of the present invention is to provide a marking tape or sheet having flexibility, excellent followability to an adherend and excellent cutability, and a method for producing the same, in view of the above-described drawbacks.
Another object is to provide a marking tape or sheet excellent in colorability, weather resistance and the like, and a method for producing the same.

The present invention provides a pressure-sensitive adhesive on one surface of a urethane resin layer obtained by reacting and curing 100 parts by weight of a polyol component and a polyisocyanate component A part by weight of a crosslinking point distance (weight average molecular weight / isocyanate group number) of 220 to 570. A marking tape or sheet in which layers are laminated, wherein A is represented by the following formula:
A = 100aX / Y
(Wherein, a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, Y is the weight percent of the isocyanate group in the polyisocyanate component)
It is a marking tape or sheet having a 2% elongation strength of 0.40 to 2.20 kg / 15 mm width and a breaking elongation of 50 to 300% at 5 ° C and 35 ° C.
The present invention is described in detail below.

The first aspect of the present invention is an adhesive tape or sheet (hereinafter referred to as “adhesive sheet”) having specific mechanical properties, in which an adhesive layer is laminated on one surface of a urethane resin layer comprising a polyol component and a polyisocyanate component. is there.

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, for example, , Polyether polyols, polyester polyols, acrylic polyols, and the like, and acrylic polyols having excellent coating film adhesion, chemical resistance, weather resistance and the like are preferably used.

Examples of the acrylic polyol include a copolymer of a hydroxyl group-containing (meth) acrylate and an alkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. preferable.

The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having an alkyl group having 12 or less carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, etc., may be copolymerized alone, Two or more kinds may be combined and copolymerized.

Further, if necessary, monomers such as styrene, vinyl acetate, vinyl propionate, (meth) acrylonitrile, N-vinylpyrrolidone and (metha) which can be copolymerized with the above hydroxyl group-containing (meth) acrylate and alkyl (meth) acrylate. ) Monomers having polar groups such as acrylic acid, maleic acid, fumaric acid, itaconic acid, (meth) acrylamide, etc. may be copolymerized. Further, two or more kinds of copolymers may be used in combination as required.

The glass transition temperature (Tg) of the polyol component is preferably 0-100 ° C., more preferably 30-80 ° C., because the urethane resin obtained becomes soft and mechanical strength decreases when it becomes low and becomes brittle when it becomes high. .

Moreover, when the hydroxyl value of the polyol component is low, the crosslinking density of the resulting urethane resin is low, softening and mechanical strength is lowered, and when it is high, the crosslinking density of the resulting urethane resin is high and brittle. Is preferred.

In addition, the hydroxyl value in this invention means the quantity (mg) of potassium hydroxide required in order to neutralize the acetic acid couple | bonded with the acetylation thing obtained from 1 g of polyol components.

Moreover, the weight average molecular weight of a polyol component will not be specifically limited if the said Tg and hydroxyl value are satisfied, and if it can melt | dissolve in a solvent, Generally it is 1,000-500,000.

The polyisocyanate component is a polyisocyanate having two or more isocyanate groups in the molecule and reacting with the polyol component to form a urethane resin, and a polyisocyanate having a distance between cross-linking points of 220 to 570 is used. The distance between the crosslinking points of the polyisocyanate is a value obtained by grading the weight average molecular weight of the polyisocyanate by the number of isocyanate (NCO) groups of the polyisocyanate, and when using two or more types of polyisocyanates in combination. The value obtained by arithmetically averaging the distance between crosslinking points of each polyisocyanate by weight ratio.

When the distance between the cross-linking points of the polyisocyanate is increased, the distance between the cross-linked polyol and the polyol is increased, and the obtained urethane resin is softened. When the distance is decreased, the distance is reduced, and the obtained urethane resin is hard and brittle. Accordingly, a polyisocyanate having a distance between cross-linking points adjusted to 220 to 570 is used, and preferably a polyisocyanate having a distance of 250 to 550 is 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 tetramethylxylene diisocyanate; trimethylolpropane adduct of diisocyanate; biuret of diisocyanate; isocyanurate of diisocyanate and condensates thereof, etc., and a mixture thereof may be used. Examples of the polyisocyanate having a distance between cross-linking points of less than 200 that are actually sold include Sumitomo Bayer Urethane Co., Ltd., trade name Sumijour N3200 (solid content concentration of 100% by weight, mainly HDI burette, weight average molecular weight 670). , Isocyanate group number 3.7, distance 181 between cross-linking points, isocyanate group content 23.0% by weight).

Polyisocyanates having a distance between cross-linking points of 220 to 570 include the above-mentioned diisocyanate and trimethylolpropane adduct, those obtained by adding polyester diol between the trimethylolpropane of the isocyanate, and addition of diisocyanate and polyester diol or polyester polyol. Products, diisocyanate biurets, diisocyanate isocyanurates, condensates thereof or mixtures thereof are preferred.

Examples of the polyisocyanate having a distance between crosslinking points of 220 to 570 which are actually sold include the following.

For example, the product name Sumidur HT manufactured by Sumitomo Bayer Urethane Co., Ltd. is an ethyl acetate solution mainly composed of an HDI adduct to trimethylolpropane (solid content concentration 75% by weight, weight average molecular weight 1100, isocyanate group number 4.5, crosslinking point The distance between them is 244, and the isocyanate group content is 13.0% by weight. The product name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd., is an ethyl acetate solution (solid content concentration 75) mainly composed of an adduct of HDI to trimethylolpropane. Weight%, weight average molecular weight 850, number of isocyanate groups 3.4, distance between cross-linking points 250, isocyanate group content 12.8% by weight), manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate HLS is a lactone of Coronate HL. Ethyl acetate solution mainly composed of cross-linked ester (solid content concentration 75% by weight, Molecular weight 900, isocyanate groups 2.3, between crosslinks distance 391, is an isocyanate group content of 10.0 wt%).

In addition, there are Sumitomo Bayer Urethane Co., Ltd., trade name Desmodule E3265, Asahi Kasei Co., Ltd., trade name Duranate E-402 and the like.

Examples of the polyisocyanate having a distance between cross-linking points exceeding 570 include trade name Desmodur TPLS 2010/1 manufactured by Sumitomo Bayer Urethane Co., Ltd. This is a polymer of HDI (solid content concentration 100% by 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 100 parts by weight of the polyol component and A part by weight of the polyisocyanate component A. A is represented by the following formula.
In the formula A = 100aX / Y, 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 of the hydroxyl group of the polyol component and the isocyanate group of the polyisocyanate component. When the isocyanate group is small (when the addition amount of the polyisocyanate component is small), the crosslinking density is low and the residual hydroxyl group is large. Therefore, the obtained urethane resin layer becomes soft and sticky, and the mechanical strength becomes insufficient. Conversely, when the isocyanate group is increased (when the amount of the polyisocyanate component is increased), the crosslinking density is increased. Since the deformation followability is lowered or the excess isocyanate groups remain and the mechanical strength easily changes with time, the polyisocyanate component is added in the above range, and the preferred range of a is 0.075 to 0.125. It is.

As the pressure-sensitive adhesive, any conventionally known pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, silicon-based pressure-sensitive adhesive, and urethane-based pressure-sensitive adhesive can be used, and the pressure-sensitive adhesive sheet of the present invention is used as a marking sheet. In this case, an acrylic pressure-sensitive adhesive having excellent weather resistance is preferable because it is often used outdoors.

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

The pressure-sensitive adhesive sheet of the present invention is formed by laminating a pressure-sensitive adhesive layer on one surface of the urethane resin layer. However, when the thickness of the urethane resin layer is thin, it becomes soft and loose and difficult to handle. 30 to 120 μm is preferable, and 40 to 100 μm is more preferable, since the followability to the surface is lowered and it becomes difficult to stick.

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

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

The mechanical properties of the pressure-sensitive adhesive sheet of the present invention are required to have a strength at 2% elongation of 0.40 to 2.20 kg / 15 mm width at 5 ° C. and 35 ° C. and a breaking elongation of 50 to 300%. It is.

When affixing the adhesive sheet while slightly stretching it to follow the adherend, if the extension strength is too weak, it will be unnecessarily stretched and difficult to apply, and if it is too strong, it will be difficult to extend and difficult to follow. Even if it can be pasted, it will be peeled off over time and it will be easy to lift, so the adhesive sheet is generally used at room temperature, that is, at 5 ° C and 35 ° C, the strength at 2% elongation is 0.40 to 2.20 kg / 15 mm. The width needs to be 0.50 to 2.10 kg / 15 mm.

In addition, the measuring method of the intensity | strength at the time of 2% expansion | extension in this invention measures the stress at the time of extending | stretching 2% by hold | maintaining a 15 mm width adhesive sheet at 100 mm space | interval, pulling at a tension speed of 200 mm / min.

Also, the elongation at break should be 50-300%, preferably 70-250%, because if it is small, it will break when stuck while stretching, or it will break on impact, and if it is too large it will be difficult to cut. is there.

In addition, the measuring method of the breaking elongation in this invention hold | maintains a 15 mm width adhesive sheet at 100 mm space | interval, it is pulled until the adhesive sheet breaks at a pulling speed of 200 mm / min, and the elongation when the adhesive sheet is cut. The obtained length was expressed as a ratio (%) to the original pressure-sensitive adhesive sheet.

Further, the residual stress of the pressure-sensitive adhesive sheet is likely to be lifted or peeled off over time if a large amount of residual stress remains after being stretched and pasted. % Or less is preferable.

The method for measuring the residual stress rate in the present invention is to hold a 15 mm wide adhesive sheet at 100 mm intervals, pull it at a pulling rate of 200 mm / min, hold 10%, and then hold it as it is. Was measured and expressed as a ratio (%) to the stress at the time of 10% elongation.

2nd this invention is an adhesive sheet by which an olefin resin layer is laminated | stacked between the urethane resin layer and adhesive layer of the adhesive sheet of 1st this invention.

Examples of the olefin resin include polyethylene resin, polypropylene resin, ethylene-propylene copolymer, ethylene or propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methyl. Any conventionally known olefinic resin such as a copolymer with an α-olefin such as -1-pentene, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, and the like can be used.

When the olefin-based resin layer is laminated, the mechanical properties of the pressure-sensitive adhesive sheet are almost governed 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 are preferably in the following range.

That is, the strength at 2% elongation at 5 ° C. and 35 ° C. is 0.40 to 2.10 Kg / 15 mm width, and the elongation at break is preferably 100% or more. Furthermore, if a large amount of residual stress remains after being stretched and stuck, it tends to be lifted or peeled off over time, so that it is preferably 10% elongated and the stress remaining rate after 10 minutes is preferably 60% or less. .

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

The weight average molecular weight is preferably 80,000 to 500,000, more preferably 200,000 to 400,000, since the film strength decreases as the weight average molecular weight decreases and the film becomes harder and decreases in flexibility when it increases. In the cross fractionation method, a flexible resin is eluted at a low temperature, and a hard resin is eluted at a higher temperature. Therefore, a polypropylene resin from which the resin is eluted in the above range is preferable.

In the second aspect of the present invention, the cross fractionation method is as follows. First, a polypropylene resin to be measured is dissolved in 140 ° C. or o-dichlorobenzene at a temperature at which it completely dissolves, cooled at a constant rate, and then a thin resin layer is formed on the surface of an inert carrier prepared in advance. They are formed in descending order of 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 with temperature is measured.

In order to adjust the 2% elongation strength and elongation at break of the olefin-based resin layer, the weight average molecular weight is 80,000 to 500,000, and the elution amount at 0 ° C. by the cross fractionation method is 0 of all resins. Polypropylene resin (hereinafter referred to as "elution amount") of 20 to 20% by weight, elution amount of 0 to 70 ° C or less and 5 to 30% by weight of all resins, and elution amount of more than 70 ° C to 70 to 90% of all resins Polypropylene resin (B)) may be used in combination with polypropylene resin (A).

Polypropylene resin (B) has a large amount of elution at over 70 ° C., 70 to 90% by weight of the total resin, and is harder and higher in mechanical strength than polypropylene resin (A). When added, the strength at 2% elongation of the olefin-based resin layer is increased, the breaking elongation is decreased, the elongation is increased by 10%, and the residual stress rate after 10 minutes is increased, so that the polypropylene-based resin (A) is 100 to 100%. The polypropylene resin (B) is preferably 0 to 70% by weight at 30% by weight.

The configuration 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 strength at 2% elongation, elongation at break and residual stress ratio are the same as those of the pressure-sensitive adhesive sheet of the first invention.

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-based resin layer and a pressure-sensitive adhesive layer laminated on the other surface. 20 to 80 μm is preferable, and 30 to 70 μm is more preferable. When the thickness of the urethane resin layer is thin, it becomes soft and loose and difficult to handle, and when it is thick, it becomes hard and the followability to the adherend is reduced, making it difficult to stick. Therefore, it is preferably 5 to 50 μm, more preferably 10 to 30 μm. It is.

Therefore, 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.

Moreover, the thickness of an adhesive layer should just be a thickness with which an adhesive sheet can be stuck enough to a to-be-adhered body, and is generally 10-80 micrometers, Preferably it is 20-50 micrometers.

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

The pressure-sensitive adhesive sheet of the present invention may be colored by adding a colorant 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 to add a colorant to the urethane resin layer.

As the colorant, any colorant used for coloring resins, paints and the like can be used. For example, azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium ion dyes, and the like; calcium carbonate, Inorganic pigments such as barium sulfate, zinc oxide, titanium oxide, chromium yellow, cadmium yellow, nickel titanium yellow, bengara, cadmium red, molybdenum orange, bitumen, ultramarine, carbon black; azo pigments, phthalocyanine pigments, metal complex pigments, Examples thereof include organic pigments such as triphenylmethane pigments, quinacdolin pigments, and isoindolinone pigments. These colorants may be used alone or in combination of two or more.

The addition amount of the colorant may be appropriately determined as necessary, but generally 0.1 to 70 parts by weight is preferably added to 100 parts by weight of the urethane resin.

Moreover, a light stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an antiblocking agent, and the like may be added to each layer as necessary.

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-succinate Examples thereof include hindered amine light stabilizers such as hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate. These light stabilizers are commercially available from Ciba Specialty Chemicals under the trade names Kima Soap 944, Tinuvin 622 and Tinuvin 123, respectively.

When the light stabilizer is added to the urethane resin layer, the hydrogen of the amine group is substituted so that the amine group does not inhibit the urethane crosslinking reaction, and the nitrogen is linked to the alkyl group or main chain, so-called NR type and A so-called NOR type in which hydrogen of an amine group is substituted and nitrogen is connected to an alkyl group or a main chain via oxygen is preferable, and tinuvin 622 and tinuvin 123 are preferably used.

Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers such as Ciba Specialty Chemicals, trade names such as Tinuvin 327 and Tinuvin 328, benzophenone ultraviolet absorbers such as Ciba Specialty Chemicals, trade name Kimasoap 81, and Ciba. Examples include triazine-based ultraviolet absorbers such as trade name Tinuvin 900 manufactured by Specialty Chemicals.

Examples of the antioxidant include hindered phenol-based antioxidants such as trade names Irganox 1010 and Irganox 1076 manufactured by Ciba Specialty Chemicals, and phosphorus-based antioxidants manufactured by Asahi Denka Co., Ltd. and trade names ADK STAB PEP8. Etc.

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.

Examples of the anti-blocking agent include inorganic fine powders such as silica and alumina, glass beads, and silicone fine particles.

The production method of the pressure-sensitive adhesive sheet of the first and second inventions is not particularly limited, and may be produced by any conventionally known method, but the pressure-sensitive adhesive sheets of the third to fifth inventions described in detail below are used. It is preferable to manufacture by a manufacturing method.

3rd this invention is a manufacturing method of the adhesive sheet of 1st this invention, The process of obtaining the 1st laminated body by which an adhesive layer is laminated | stacked on the one surface of 1st release paper, 100 weight of polyol components A reactive resin composition comprising a part, a polyisocyanate component A part by weight and a solvent is applied to the second release paper and dried, and a urethane resin layer having a crosslinking rate of 20 to 93% is formed on one surface of the second release paper. A step of obtaining a second laminate formed, and the first laminate and the second laminate so that the pressure-sensitive adhesive layer of the first laminate and the urethane resin layer of the second laminate are in contact with each other. It consists of the process of laminating the bodies and completing 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. As the first release paper, any release paper generally used as release paper such as an adhesive sheet and an adhesive label can be used. For example, polyethylene is laminated on a paper substrate such as fine paper and kraft paper. Polyethylene laminated paper; clay-coated paper in which clay is laminated on a paper base such as fine paper, kraft paper; glassine paper; super calendered paper; plastic film such as polyethylene terephthalate film, stretched polypropylene film, polyethylene film, etc. Release paper in which a release agent such as a silicone release agent, an alkyl pendant release agent, or a fluorine release agent is laminated on a base material can be used.

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

In the step of obtaining the second laminate, the reactive resin composition is applied to the second release paper and dried, and a urethane resin layer having a crosslinking rate of 20 to 93% is formed on one surface of the second release paper. It is a process to.

The reactive resin composition is composed of 100 parts by weight of a polyol component, A part by weight of a polyisocyanate component A, and a solvent. The polyisocyanate does not use a so-called block type in which isocyanate is blocked with an alcohol such as phenol or cyclohexanone oxime. In this case, since the reaction proceeds rapidly when the polyol component and the polyisocyanate component are mixed, the polyol solvent solution and the polyisocyanate solvent solution are prepared separately, and both are mixed to obtain a reactive resin composition, It is preferable to apply and dry the second release paper.

As the solvent, any solvent can be used as long as it can dissolve the polyol component and the polyisocyanate component, and examples thereof include ethyl acetate, toluene, xylene, butyl acetate, isobutyl acetate, and methyl isobutyl ketone. . Further, a mixed solvent may be used, and examples of the commercial product include a product name Solvesso manufactured by Exxon Chemical.

The concentration of the polyol solvent solution may be appropriately determined. However, since the polyol component is a high molecular weight substance, when the concentration is high, the viscosity becomes high and mixing and coating become difficult. Therefore, the solid content is preferably 25 to 100% by weight. The concentration of the polyisocyanate solvent solution may be appropriately determined. However, since the polyisocyanate component has a low molecular weight and low viscosity, a high concentration is preferable so that the mixing efficiency with the polyol component is good and the drying efficiency is good. 50 to 100% by weight is preferable.

When a colorant, a light stabilizer, an ultraviolet absorber, an antioxidant, or the like is added to the urethane resin layer, it is preferably added to the polyol solvent solution and dissolved or dispersed and mixed.

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

Although the addition amount of a catalyst should just be determined suitably as needed, generally it is 0.05-1.0 weight part with respect to 100 weight part of total amounts of a polyol component and a polyisocyanate component.

Since the reactive resin composition applied to the second release paper takes time to crosslink, the amount of air is increased at a low temperature below the boiling point so that the solvent does not boil and foam in the initial stage. After the solvent is volatilized to a certain degree, it is preferably heated to a temperature equal to or higher than the boiling point to promote the progress of crosslinking and to reduce the residual solvent.

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

The crosslinking rate is the ratio of the filtrate to the initial urethane resin when the urethane resin is supplied to a shaker, swollen and dissolved in ethyl acetate at 23 ° C. for 24 hours, and then filtered through a 200-mesh wire mesh. (% By weight).

As described above, the reaction rate of the reactive resin composition becomes slower as the reaction progresses, so a great amount of heat and time are required to complete the reaction of the reactive resin composition continuously in the manufacturing process. However, productivity is poor, but by taking the above steps, it can be manufactured with high productivity.

The second release paper is not particularly limited, and the release paper detailed as the first release paper can be used, and the physical adhesiveness of the urethane resin (reactive resin composition) is the pressure-sensitive adhesive. Since it is low in comparison, a film having a low polarity without reacting with an isocyanate group of the urethane resin layer (reactive resin composition), for example, a plastic film such as a polypropylene film, a polyethylene terephthalate film, a polyethylene film, and a stretched film thereof Can be used.

The second release paper is a so-called process paper, and is used by peeling the adhesive sheet after curing to the adherend before or after sticking. The urethane resin layer and the second release paper after completion of the reaction are used. When the adhesiveness between the urethane resin layer and the second release paper is increased, the above four-layer laminate is transported, wound, and cured and stored during secondary processing. Occurs and the appearance of the urethane resin layer becomes poor. On the other hand, when the size is increased, it becomes difficult to peel off the second release paper, and the second release paper may be broken or the peeling may be intermittent, resulting in a step mark on the urethane resin layer, resulting in poor appearance. Become.

Accordingly, the second release paper is preferably release paper having a 180-degree peel strength of 5 to 200 g / 50 mm width measured at a peel speed of 300 mm / min after completion of the reaction of the urethane resin. “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 affixed to an adherend, but when used as a marking sheet, design properties may be required. In the above production method, the urethane resin is applied and dried as a reactive resin composition on the second release paper, and the second release paper is peeled off after the reaction of the urethane resin is completed. The surface shape of the release paper is transferred. Therefore, it is preferable to use a smooth release paper when the surface of the urethane resin layer is required to be smooth, and mat processing is required when the surface of the urethane resin layer is required to be matt. It is preferable to use a release paper whose surface has been subjected to uneven processing by a process such as roll processing or sand blasting.

4th this invention is a manufacturing method of the adhesive sheet of 2nd this invention, and obtains the 1st laminated body by which an adhesive layer and a 1st release paper are laminated | stacked sequentially on one surface of an olefin resin layer. A reactive resin composition comprising a step, 100 parts by weight of a polyol component, A part by weight of a polyisocyanate component, and a solvent is applied to the second release paper and dried, and a crosslinking rate of 20 to 93 is formed on one surface of the second release paper. % Of the urethane resin layer is formed, and the olefin resin layer of the first laminate and the urethane resin layer of the second laminate are in contact with each other. It consists of the process of laminating | stacking a laminated body and a 2nd laminated body, and completing reaction of a 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 resin layer. The formation method of each layer is not particularly limited, and any method may be employed. For example, (1) co-extrusion of an olefin resin and a hot-melt type adhesive, and a first release paper is laminated on the adhesive layer (2) As described in detail in the third aspect of the present invention, a method in which an adhesive layer is formed on the first release paper, and then a separately formed olefin resin film is superposed, (3) First, an olefin Examples thereof include a method of preparing a resin-based resin film, laminating a pressure-sensitive adhesive layer on one surface, and superimposing 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 aspect of the present invention. Next, in the third aspect of the present invention, the first laminate and the second laminate are laminated so that the olefin resin layer of the first laminate and the urethane resin layer of the second laminate are in contact with each other. As detailed, the reaction of the urethane resin is completed.

5th this invention is a manufacturing method of the adhesive sheet of 2nd this invention, and obtains the 1st laminated body by which an adhesive layer and a 1st release paper are laminated | stacked sequentially on one surface of an olefin resin layer. A process and a reactive resin composition comprising 100 parts by weight of a polyol component, A part by weight of a polyisocyanate component, and a solvent are applied to the olefin resin layer and dried to form a urethane resin layer having a crosslinking rate of 20 to 93%. Then, the second release paper is laminated on the urethane resin layer to complete the reaction of the urethane resin.

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

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

Finally, the second release paper is laminated on the urethane resin layer crosslinked to 20 to 93% to complete the reaction of the urethane resin. The second release paper is laminated by pressing the second release paper on the urethane resin layer of a four-layer laminate in which the first release paper, the pressure-sensitive adhesive layer, the olefin resin layer, and the urethane resin layer are sequentially laminated. However, it is preferable that the pressure is superimposed and pressed at a temperature near the glass transition temperature of the urethane resin. The method for completing the reaction of the urethane resin is as described in detail in the third aspect of the present 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, any of the urethane resin layer and the olefin resin layer is used. Either or both of them may be subjected to surface polarity imparting treatment such as corona discharge treatment or flame treatment, or an undercoat agent generally used as an undercoat agent for adhesive tape may be laminated.

In addition, any lamination 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. Examples of the method include pressing after overlapping the layers, and pressing while heating with a heating roll after overlapping both layers.

Since the structure of the pressure-sensitive adhesive tape or sheet of the present invention is as described above, it is flexible, has excellent conformability to the unevenness and curved surface of the adherend, and has excellent cut performance. Moreover, since it does not contain chlorine, dioxins are not generated even when incinerated, and there is no problem in environmental hygiene. Therefore, it can be suitably used particularly as a marking tape or sheet.
Moreover, since the manufacturing method of the adhesive tape or sheet | seat of this invention is as the above-mentioned, an adhesive tape or sheet | seat can be manufactured easily.

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

First, materials used in the examples will be described first. In the examples, acrylic polyols, polyisocyanates, olefin resins, and release papers are indicated by the following abbreviations.

Acrylic polyols Acrylic polyols A1, A2, A4 and A5 are ethyl acetate solutions of copolymers of predetermined amounts of monomers shown in Table 1. The copolymer concentration was 40% by weight, and the glass transition temperature Tg and hydroxyl value are shown in Table 1.

Acrylic polyol A3 is a copolymer comprising 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 ( Ethyl acetate solution (manufactured by Nippon Paint Co., Ltd.) of 100 parts by weight of an ethyl acetate solution (hydroxyl value 70 mg / g) (copolymer concentration is 40% by weight) and caprolactone-modified polyester diol (hydroxyl value 45 mg / g, weight average molecular weight about 2000) , Trade name Softener 5, diol concentration 75% by weight).
The glass transition temperature Tg and the hydroxyl value are shown in Table 1.

Using a mixture of a polyisocyanate and a predetermined amount of polyisocyanate indicated in polyisocyanate <br/> Table 2. Table 2 shows the distance between cross-linking points.

ＨＬＳ；日本ポリウレタン社製、商品名コロネートＨＬＳ
ＨＬ；日本ポリウレタン社製、商品名コロネートＨＬ
Ｎ３２００；住友バイエルウレタン社製、商品名スミジュールＮ３２００
ＴＰＬＳ；住友バイエルウレタン社製、商品名デスモジュールＴＰＬＳ２０１０／１

HLS: Nippon Polyurethane, trade name Coronate HLS
HL; manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate HL
N3200; manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name Sumijour N3200
TPLS: Sumitomo Bayer Urethane Co., Ltd., trade name Death Module TPLS2010 / 1

Olefin resin The elution amount and weight average molecular weight of the olefin resin used for forming the olefin resin layer by the cross fractionation method are shown in Table 3.

ＫＳ；ポリプロピレン樹脂、モンテルエスディケイサンライズ社製、商品名アドフレックスＫＳ０８１Ｐ
Ｍ４０；線状低密度ポリエチレン、東ソー社製、商品名ニポロンＬ−Ｍ４０
ＰＰ；ポリプロピレン樹脂、日本ポリオレフィン社製、商品名ＪアロマーＰＣ６３０Ｓ
ＥＢＲ；エチレンブテン共重合体、住友化学工業社製、商品名エスプレンＮＯ４１６

KS: Polypropylene resin, manufactured by Montelu SDK 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., Ltd., trade name: J Aroma PC630S
EBR; ethylene butene copolymer, manufactured by Sumitomo Chemical Co., Ltd., trade name: Esprene NO416

Copolymer (7% by weight of adhesive n-butyl acrylate, 20.0% by weight of 2-ethylhexyl acrylate, 9.7% by weight of acrylic acid and 0.3% by weight of 2-hydroxyethyl acrylate) To 100 parts by weight of 30 wt% ethyl acetate solution having a weight average molecular weight of 600,000 and weight average molecular weight / number average molecular weight = 4.5), an isocyanate-based crosslinking agent (trade name Coronate L-55E, manufactured by Nippon Polyurethane Co., Ltd., solid content concentration) A 55% ethyl acetate solution) (1.0 part by weight) was mixed and used as an adhesive.

Colorant <br/> Ciba Specialty Chemicals, trade name Chromothal DPP Red BP

Release paper C1; double-sided polyethylene laminated paper with one side subjected to silicone release treatment, manufactured by Kite Chemical Industry Co., Ltd., trade name Smilies SLK-110AW
C2; Stretched polypropylene film, manufactured by Futamura Chemical Co., Ltd.
C3: Paper treated with alkyd resin on both sides, manufactured by Lintec Co., Ltd., trade name Koutashi ES160
C4: stretched polypropylene film processed with matte, manufactured by Futamura Chemical Co., Ltd., trade name: Dazai FOR-MP2
C5: Polyethylene terephthalate film treated with alkyd resin on both sides, manufactured by Teijin Limited, trade name Tetron film S-PZ
C6: Polyethylene terephthalate film with silicone release treatment on both sides, manufactured by Teijin Limited, trade name BUREX

Next, methods for measuring physical properties and the like will be described. The methods for measuring the hydroxyl value of the polyol component, the crosslinking rate of the urethane resin, the strength at 2% elongation, the elongation at break, the residual stress rate, the cross fractionation, and the 180 ° peel strength between the urethane resin layer and the second release paper are invented. In the detailed disclosure column.

The curable <br/> obtained pressure-sensitive adhesive sheet was supplied 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 adhesion ×: Gauze adhesion

Preservability Gauze was pressed against the urethane resin layer of the obtained pressure-sensitive adhesive sheet so that the load was 10 g / cm ² , allowed to stand at 40 ° C. for 24 hours, then gauze was removed, and the surface of the urethane resin layer was observed.
○: No significant change in surface gloss △: Some change in surface gloss x: Large change in surface gloss

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

Pasting property After the obtained adhesive sheet was stretched between the tops of aluminum corrugated plates having a radius of curvature of 20 mm and a depth of 15 mm, the adhesive sheet was pressed and pasted into the valley portion while being pasted. 23 After leaving at 1 ° C. for 1 week, the pressure-sensitive adhesive sheet was observed to be peeled off (floated).
○: Floating 1 mm or less in width Δ: Floating around the bottom ×: Floating over the whole surface, cracked adhesive sheet that did not follow when affixed

Workability A 100 mm square pressure-sensitive adhesive sheet was attached to an aluminum plate, and the attached state was observed.
○: Can be pasted without wrinkles △: Wrinkles were easy to paste ×: Wrinkled

Weather resistance The obtained pressure-sensitive adhesive sheet was supplied to a sunshine weather meter, and the surface state after 2000 hours exposure was observed.
○: Almost no change Δ; slightly discolored, with a difference in glossiness ×; apparently different appearance

Combustion chlorine generation test The obtained 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).
○: Chlorine could not be detected ×: Chlorine could be detected

Adhesion Supply the obtained adhesive sheet to a sunshine weather meter, and after exposure for 1000 hours, in accordance with the JIS-K5400 cross-cut evaluation method, cut 10 mm square adhesive sheets every 1 mm, 100 pieces Then, the cellophane tape was pressure-bonded and peeled off, and the urethane resin layer peeled off was counted.
○: No peeling Δ; 1 to 25 peeled cells ×: 26 or more peeled cells

Examples 1-6, Comparative Examples 1-6
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 obtain a first laminate in which a pressure-sensitive adhesive layer having a thickness of 30 μm was formed.

A predetermined amount (solid content) of acrylic polyol, polyisocyanate, colorant and catalyst (dioctyltin dilaurate, trade name Stan SNT-1F, trade name Stan SNT-1F) shown in Table 4 and Table 5 and A compound obtained by mixing 1 part by weight of a light stabilizer (trade name Tinuvin 622, manufactured by Ciba Specialty Chemicals Co., Ltd.) was applied to the second release paper C2 with a baker type applicator and dried in a hot air oven at 110 ° C. for 5 minutes. The 2nd laminated body in which the urethane resin layer of the predetermined thickness shown in Table 4 and Table 5 was formed was obtained.

The pressure-sensitive adhesive layer of the obtained first laminate and the urethane resin layer of the second laminate were superposed and laminated by pressing with a heating roll at a temperature of 100 ° C. to obtain a pressure-sensitive adhesive sheet. After the obtained pressure-sensitive adhesive sheet was cured at 40 ° 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 during lamination and the 180-degree peel strength of the second release paper C2 were measured, and the results are shown in Tables 4 and 5.

Comparative Example 7
100 parts by weight of a vinyl chloride resin (trade name PHS-10, manufactured by Kaneka Chemical Co., Ltd.), 7 parts by weight of a colorant, 30 parts by weight of an adipate plasticizer (trade name: Adeka Sizer PN300, manufactured by Asahi Denka Kogyo Co., Ltd.) A sol obtained by mixing 5 parts by weight of a barium / zinc composite heat stabilizer (trade name MARK SC34, manufactured by Asahi Denka Kogyo Co., Ltd.) and 150 parts by weight of a mixed solvent (trade name, Solvesso, manufactured by Exxon Chemical Co., Ltd.) is used as a release paper. On C3, it 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 vinyl chloride resin film having a thickness of 50 μm.

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 with it, and was laminated by pressing with a heating roll at a temperature of 100 ° C. to obtain a pressure-sensitive adhesive sheet. It was. After the obtained pressure-sensitive adhesive sheet was cured 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.

Examples 7-12, 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, 0.007 parts by weight of antioxidant (trade name: Irganox 1076, manufactured by Ciba Specialty Chemicals) and light stabilizer ( A compound consisting of 0.021 parts by weight of Ciba Specialty Chemicals Co., Ltd., trade name Tinuvin 622) was supplied to an extruder and extruded with a T-die at 230 ° C. (200 ° C. only in Example 7). An olefin resin film having the indicated thickness was obtained. 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 corona discharge treatment, and the surface energy of the film was adjusted to 45 dynes with the measured value of the wetting reagent.

The pressure-sensitive adhesive is 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. The olefin resin film is superimposed on this pressure-sensitive adhesive layer. Thus, a first laminate was obtained.

A predetermined amount (solid content) of acrylic polyol, polyisocyanate and colorant and catalyst (dioctyltin dilaurate, trade name Stan SNT-1F, trade name Stan SNT-1F) shown in Table 6 and Table 7 and A compound in which 1 part by weight of a light stabilizer (trade name: Tinuvin 622, manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed was applied to the olefin resin film surface of the first laminate with a baker type applicator and heated in a hot air oven at 110 ° C. After drying for a minute, 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. After the obtained pressure-sensitive adhesive sheet was cured at 40 ° C. 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 crosslinking rate of the urethane resin and the 180 degree peel strength of the release paper C2 when the release paper C2 was laminated were measured, and the results are shown in Tables 6 and 7.

Comparative Example 9
100 parts by weight of a vinyl chloride resin (manufactured by Kaneka Chemical Co., Ltd., trade name PHS-10), 30 parts by weight of titanium oxide powder (trade name: DISCOL DAP050 White, manufactured by Dainichi Seika Kogyo Co., Ltd.), adipate plasticizer ( Asahi Denka Kogyo Co., Ltd., trade name Adeka Sizer PN300) 30 parts by weight, barium / zinc composite heat stabilizer (Asahi Denka Kogyo Co., Ltd., trade name MARK SC34) 5 parts by weight and mixed solvent (Nippon Mining Co., Ltd., trade name) Solvesso) The sol obtained by mixing 150 parts by weight was applied to release paper C3 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. A vinyl chloride resin film having a thickness of 40 μm was obtained. The physical properties of the obtained vinyl chloride resin film were measured, and the results are shown in the physical property column of the olefin resin layer in Table 7.

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

The pressure-sensitive adhesive is 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. The vinyl chloride resin film is overlaid on the pressure-sensitive adhesive layer. Together, a first laminate was obtained.

A predetermined amount (solid content) of acrylic polyol, polyisocyanate, colorant and catalyst (dioctyltin dilaurate, trade name Stan SNT-1F, trade name Stan SNT-1F) and light stabilizer shown in Table 7 (Product name: Tinuvin 622, manufactured by Ciba Specialty Chemicals Co., Ltd.) A blend of 1 part by weight was applied to the vinyl chloride resin film surface of the first laminate with a baker-type applicator and dried in a hot air oven at 110 ° C. for 5 minutes. Then, a urethane resin layer having a thickness of 20 μm was formed, and then a release paper C2 was laminated on the urethane resin layer to obtain an adhesive sheet. After the obtained pressure-sensitive adhesive sheet was cured 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 ratio of the urethane resin and the 180 degree peel strength of the release paper C2 when the release paper C2 was laminated were measured, and the results are shown in Table 7.

Comparative Example 10
100 parts by weight of an olefin resin shown in Table 7, 3.5 parts by weight of titanium oxide powder, 0.007 parts by weight of an antioxidant (manufactured by Ciba Specialty Chemicals, trade name: Irganox 1076) and a light stabilizer (Ciba Specialty Chemicals) A compound consisting of 0.021 part by weight of a trade name, Tinuvin 622) was supplied to an extruder and extruded with a T die at 230 ° C. to obtain an olefin resin film having a thickness of 50 μm. The physical properties of the obtained olefin resin film were measured and the results are shown in Table 7.

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

The pressure-sensitive adhesive is 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. The corona discharge of the olefin resin film is applied to the pressure-sensitive adhesive layer. The treated surfaces were superposed 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.

Examples 13 to 15 and Comparative Examples 11 and 12
In the same manner as in Example 1, the pressure-sensitive adhesive was applied to the first release paper C1 and dried to obtain a first laminate.

The composition for urethane resin used in Example 3 was applied to the second release paper shown in Table 8 so that the urethane resin layer had a thickness of 50 μm, and dried at a furnace length of 35 m and a furnace temperature of 100 ° C. A second laminate was obtained by supplying to the furnace at the feed rate shown in Table 8 and drying.

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

Further, the cross-linking ratio of the urethane resin during lamination and the 180 degree peel strength of the second release paper C2 were measured, and 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.

Example 16
A first laminate was obtained in the same manner as in Example 9. On the other hand, the compound 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 was applied to a drying furnace having a furnace length of 35 m and a furnace temperature of 100 ° C. , Supplied at a feed rate of 20 m / min and dried to obtain a second laminate.

The pressure-sensitive adhesive sheet was obtained by laminating the olefin-based resin layer of the obtained first laminate and the urethane resin layer of the second laminate so that they were in contact with each other and 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 9. Further, after curing the obtained pressure-sensitive 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.

Furthermore, the crosslinking rate of the urethane resin during lamination and the 180 degree peel strength of the second release paper C2 were measured, and 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, in the same manner as in Example 9, the urethane resin composition used in Example 9 was formed on the olefin-based resin layer of the first laminate so that the thickness of the urethane resin layer was 20 μm. It was applied, supplied to a drying furnace having a furnace length of 35 m, and a furnace temperature of 100 ° C. at a predetermined feed rate shown in Table 9, and dried to obtain a second laminate.

A predetermined second release paper shown in Table 9 was superimposed on the urethane resin layer of the obtained second laminate, and laminated by pressing with a heating roll at a temperature of 100 ° C. to obtain an adhesive sheet. In addition, the temperature of the heating roll of Example 20 was normal 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. Further, after curing the obtained pressure-sensitive 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 crosslinking 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.

According to the present invention, it is possible to provide a marking tape or sheet having flexibility, excellent followability to an adherend, excellent cutability, excellent colorability, weather resistance, and the like, and a method for producing the same.

Claims (9)

A pressure-sensitive adhesive layer is laminated on one surface of a urethane resin layer obtained by reacting and curing 100 parts by weight of a polyol component and a polyisocyanate component A part by weight of a crosslinking point distance (weight average molecular weight / isocyanate group number) of 220 to 570. A marking tape or sheet, wherein A is represented by the following formula:
A = 100aX / Y
(Wherein, a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, Y is the weight percent of the isocyanate group in the polyisocyanate component)
A marking tape or sheet having a 2% elongation strength of 0.40 to 2.20 kg / 15 mm width at 5 ° C and 35 ° C and a breaking elongation of 50 to 300%. The marking tape or sheet according to claim 1, 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. The marking tape or sheet according to claim 1 or 2, wherein 0.1 to 70 parts by weight of a colorant is added to the urethane resin layer. The marking tape or sheet according to claim 1, 2 or 3, wherein the distance between cross-linking points is 250 to 550. The marking tape or sheet according to claim 1, 2, 3, or 4, wherein the urethane resin layer has a thickness of 30 to 120 µm. The marking tape or sheet according to claim 1, 2, 3, 4, or 5 having a residual stress rate of 10% or less after 10% elongation at 23 ° C. 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%. 5. The marking tape or sheet according to 5 or 6. A step of obtaining a first laminate in which an adhesive layer is laminated on one surface of the first release paper, 100 parts by weight of a polyol component, and the distance between cross-linking points calculated by dividing the weight average molecular weight by the number of isocyanate groups is 220. A reactive resin composition comprising a polyisocyanate component A of ˜570 and a solvent is applied to the second release paper and dried, and a urethane resin having a crosslinking rate of 20 to 93% is formed on one surface of the second release paper. A step of obtaining a second laminated body in which layers are formed, and the first laminated body and the second laminated body so that the pressure-sensitive adhesive layer of the first laminated body and the urethane resin layer of the second laminated body are in contact with each other. The marking tape according to claim 1, 2, 3, 4, 5 or 6, wherein the A is represented by the following formula: Sheet manufacturing method.
A = 100aX / Y
(Wherein, a is a constant; 0.067 to 0.135, X is the hydroxyl value of the polyol component, Y is the weight percent of the isocyanate group in the polyisocyanate component) The manufacturing method of the marking tape or sheet | seat of Claim 8 whose 180 degree peel strength (300 mm / min) of the 2nd release paper after completion of reaction of a urethane resin is 5-200 g / 50mm width.