JP6510192B2 - LAMINATE, SURFACE PROTECTIVE ARTICLE, AND METHOD OF MANUFACTURING LAMINATE - Google Patents

Description

  The present invention relates to a laminate. In particular, the present invention relates to a laminate using a thermoplastic resin.

  Thermoplastic resins having high impact strength, in particular thermoplastic polyurethane (TPU), have conventionally been used as substrates for protective films and the like. In particular, in Europe and the United States, under the name of paint protection film (PPF), it is widely used as a film for protecting a car body from stone splashing and scratches. An example is Scotchgard Paint Protection Film from 3M.

  As a laminate using a thermoplastic polyurethane, Patent Document 1 discloses a multilayer film used to protect the surface, in particular, the surface (for example, a painted surface) of a vehicle (for example, a car, an aircraft, a ship, etc.) Disclosed are membranes such as used for protection, and more particularly multilayer protective membranes (paragraph 0001) backed with a pressure sensitive adhesive and having a polyurethane layer on top of the thermoplastic polyurethane layer. It is done.

  These protective films (multilayer protective films) are required to have composite properties. For example, when it is peeled off from a coated plate, in addition to the addition of antifouling properties to the surface of the coated plate of a car etc., the improvement of the adhesion characteristics to the coated plate, and the improvement of heat resistance and weatherability, It is required that film and glue do not remain in the pasting place.

  In addition, these protective films can fully exhibit high-level functions, such as antifouling, and can maintain the cleanliness of the substrate surface for a long period of time. However, in the comprehensively determined product design, the foremost anti-soiling layer does not require the anti-soiling function depending on the application or the same application, and may become excessive in quality and expensive. . Furthermore, in the case of construction of a large area, in the case where the antifouling layer type of the protective film and the non-antifouling layer type coexist in each part, or in consideration of the use and the film material, the antifouling layer is omitted. There is also a possibility.

Patent No. 5426159 gazette

  Then, this invention makes it a subject to be a laminated body which can be utilized as a protective film which used the thermoplastic resin, and which is excellent in affixing property, and in which adhesive residue was controlled.

  The present inventors diligently studied to solve the above problems. As a result, when a laminate obtained by combining a thermoplastic resin and a pressure-sensitive adhesive layer with improved sticking characteristics and having no adhesive residue when peeled off is used as a protective film, the conventional protective film can not be obtained. It discovered that it became a protective film which has the outstanding effect, and completed this invention. That is, in order to maintain the antifouling layer performance (some layers may be omitted) and the thermoplastic resin film performance for a long time with the high performance, as described later, a completely new pressure-sensitive adhesive layer / pasting method is adopted. did. After use for a long time, there is no adhesive residue when peeled off because of replacement with a new protective film, taking into consideration the initial properties of the combined laminate and protective film, and the initial properties of the adhesive layer This novel adhesive application method is also useful for maintaining the mechanical properties, heat resistance properties, weather resistance, and releasability (without adhesive residue) after a long period of time well for the conventional protective film. It found that it became a protective film which has not outstanding effect, and it led to the completion of the present invention.

The laminate according to the first aspect of the present invention is, for example, as shown in FIG. 1, a base film 11 formed of a thermoplastic resin; and an adhesive layer formed on the first surface side of the base film 11 13 and the surface roughness of the adhesive layer 13 is 350 to 750 nm.
In the present specification, "on the surface side" means that they may be laminated in contact or may be laminated via other layers. "On the surface" means laminating in contact.
When it comprises in this way, it is a laminated body excellent in adhesiveness by the adhesion layer which has surface roughness 350-750 nm, Comprising: It becomes a laminated body which suppressed the adhesive residue at the time of peeling a laminated body.
The adhesive layer also serves as a buffer layer between the laminate and the surface of the adherend, and the presence of the adhesive layer without defects reduces the impact of an impact event on the adherend in the field of laminates of the above applications. It can be done.

  In the laminate 10 according to the second aspect of the present invention, in the laminate 10 according to the first aspect of the present invention, the adhesive layer 13 is at least one selected from acrylic, urethane, rubber, and silicone. Composed of two resins.

The laminate according to the third aspect of the present invention is provided on the surface of the adhesive layer 13 opposite to the base film 11 in the laminate 10 according to the first aspect or the second aspect of the present invention. The surface of the surface of the release film 14 with respect to the adhesive layer 13 has a surface roughness of 350 to 800 nm.
If comprised in this way, the surface roughness of the adhesion layer 13 can be 350-750 nm with the peeling film 14 whose surface roughness is 350-800 nm at the time of manufacture of a laminated body. Moreover, the adhesive surface of the adhesive layer 13 can be protected by the peeling film 14 after manufacture.

In the laminate 10 according to the fourth aspect of the present invention, in the laminate 10 according to the third aspect of the present invention, the pressure-sensitive adhesive layer 13 peels the uneven shape exhibiting the surface roughness after peeling off the peeling film 14 Hold for 10 to 120 minutes.
According to this configuration, when pasting to the target adherend, the defoaming proceeds rapidly while using the adhesive layer concave portions of the adjacent non-adhered parts one after another, and the adhesive surface from which the bubbles are dislodged one after another It unites and adheres to the adherend. Furthermore, after bonding, the uneven shape is easily eliminated with the aid of the applied pressure, and is uniformly bonded following the adherend.

In the laminate 10 according to the fifth aspect of the present invention, in the laminate 10 according to the third aspect or the fourth aspect of the present invention, the release film 14 has a fluorine resin on the surface with respect to the adhesive layer 13. At least one release agent selected from silicone resin and long chain carbamate is applied.
If comprised in this way, it will become easy to peel a peeling film from the adhesion layer.

The surface protection article according to the sixth aspect of the present invention comprises the laminate according to the first aspect or the second aspect of the present invention; and the article to which the laminate is attached to the surface by the adhesive layer 13 A surface protection article in which the concavo-convex shape indicating the surface roughness of the adhesive layer 13 has disappeared.
According to this structure, the coating on the surface of the article can be protected by the laminate which is uniformly attached to the article by disappearing the uneven shape. In addition, the surface can be protected from scratches and the like by the thermoplastic resin having high impact resistance. Furthermore, the pressure-sensitive adhesive layer is excellent in tackiness, excellent in heat resistance and weather resistance, and has no adhesive residue after peeling.

The method for producing a laminate according to the seventh aspect of the present invention comprises the steps of: providing a substrate film 11 formed of a thermoplastic resin; and the adhesive layer 13 on the first surface side of the substrate film 11 And forming a pressure-sensitive adhesive layer 13 having a surface roughness on the opposite side to the base film 11 of 350 to 750 nm.
If comprised in this way, the adhesive layer excellent in adhesiveness can be formed.

  By providing the laminate of the present invention, the surface of the article as an adherend can be protected by the laminate having excellent adhesion properties and suppressed adhesive residue.

It is a figure which shows the laminated constitution of the laminated body 10 which concerns on the 1st Embodiment of this invention. It is a graph which shows the relation between surface coarseness (Ra) of an adhesion side, and pasting characteristics.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same or similar reference numerals, and redundant description will be omitted. Further, the present invention is not limited to the following embodiments.

[Laminate 10]
The laminate 10 according to the first embodiment of the present invention includes a base film 11 and an adhesive layer 13 as shown in FIG. The laminate 10 is provided with the release film 14 at the time of production, but the release film 14 is peeled off and used when it is attached to the surface of an article which is an adherend.

[Base film 11]
It is desirable that the base film 11 be a film formed of a thermoplastic resin.
As thermoplastic resins, polyurethane resins, polyester resins, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, polyvinyl chloride Resins, such as system resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, norbornene resin, etc. can be mentioned. Specifically, thermoplastic polyurethane, polycaprolactone (PCL), acrylic acid polymer, polyester, polyacrylonitrile, polyether ketone, polystyrene, polyvinyl acetate or derivatives thereof are preferable. These resins may be used alone, or a plurality of resins may be used in combination.
The thickness of the base film 11 is not particularly limited, but when the present invention is used as a laminate, the thickness of the base film is preferably 50 to 300 μm, more preferably 100 to 200 μm. . The mechanical strength of a base material is enough that the film thickness of a base film is 50 micrometers or more, and it becomes possible to form a layer on a base material. Moreover, the thickness of a laminated body does not become thick too much that a film thickness is 300 micrometers or less.

  An antifouling layer may be provided on the surface s1 of the base film 11 shown in FIG. The antifouling layer can be laminated by a known method.

[Adhesive layer 13 / peeling film 14]
The adhesive layer 13 is formed by applying an adhesive to the first surface side of the base film 11, as shown in FIG. It may be formed directly on the surface of the base film 11, or may be laminated via another layer with the base film 11.
As a pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 13, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive or the like can be used. From the viewpoint of product design, in applications requiring long-term durability, acrylic pressure-sensitive adhesives excellent in heat resistance and weather resistance are preferable.
In the pressure-sensitive adhesive layer 13 of the present application, the surface of the pressure-sensitive adhesive is provided with asperities from the viewpoint of adhesion characteristics to an article to be an adherend.

Examples of acrylic pressure-sensitive adhesives include acrylic pressure-sensitive adhesives containing an acrylic copolymer obtained by copolymerizing a monomer component having a functional group such as a carboxyl group or a hydroxyl group in a monomer component mainly composed of acrylic acid ester. .
As an acrylic ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) a Lilate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, Nonadecyl (meth) acrylate, eicosyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate and the like can be mentioned. One or more of these alkyl (meth) acrylates can be used.

  The following monomer components can be copolymerized with the above alkyl (meth) acrylate. Examples of copolymerizable monomer components include carboxyl groups such as itaconic acid, maleic acid, crotonic acid, isocrotonic acid, fumaric acid, (meth) acrylic acid, carboxyethyl (meth) acrylate and carboxypentyl (meth) acrylate. Monomers containing; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) acrylic acid Hydroxyl-containing monomers such as 8-hydroxyoctyl, 10-hydroxydecyl (meth) acrylic acid, 12-hydroxylauryl (meth) acrylic acid, (4-hydroxymethylcyclohexyl) -methyl acrylate; glycidyl (meth) acrylate, methyl glycidyl Glycidyl group-containing monomers such as (meth) acrylate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acryloyl morpholine, N-vinyl-2-piperidone, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholindione, N-cyclohexyl maleimide , N-phenylmer Imide, N- acryloyl pyrrolidine, nitrogen-containing monomers such as t- butyl aminoethyl (meth) acrylate, derivatives of styrene and styrene monomers such as vinyl acetate and the like. If necessary, one or more of these monomers can be copolymerized with (meth) acrylic acid ester and used.

The pressure-sensitive adhesive used in the present invention is, for example, at least one member selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate, and at least one carboxyl group selected from the group consisting of acrylic acid and methacrylic acid. It is preferable to contain a containing monomer.
The pressure-sensitive adhesive used in the present invention was increased in glass transition temperature (Tg) by adding a hard component such as methyl acrylate and vinyl acetate to improve heat resistance and weather resistance. As a hard component used for adjustment of such a glass transition temperature, a methyl acrylate, vinyl acetate, methyl methacrylate, an acrylonitrile is mentioned.
In addition, in order to further improve various physical properties, such as weather resistance, you may add an ultraviolet absorber, a light stabilizer, etc. as needed.
The proportion of the hard component is 10 to 80% by weight, preferably 20 to 70% by weight, and more preferably 30 to 60% by weight, with respect to the total amount of the pressure-sensitive adhesive.

The weight average molecular weight (Mw) of the acrylic copolymer is 50,000 to 2,000,000, preferably 100,000 to 1,500,000, and more preferably 150,000 to 1,000,000.
The number average molecular weight (Mn) is 10,000 to 500,000, preferably 10,000 to 400,000, and more preferably 10,000 to 300,000.
The dispersion value is 1 to 20, preferably 1 to 15, and more preferably 2 to 10.
The glass transition temperature is −70 to 0 ° C., preferably −40 to 0 ° C., more preferably −30 to 0 ° C., and particularly preferably −20 to 0 ° C.

In order to apply the composition to be the adhesive layer 13 to the release film 14 or the base film 11, a gravure coating method, a bar coating method, a spray coating method, a spin coating method, a roll coating method, a die coating method which are usually performed It can be carried out by a knife coating method, an air knife coating method, a hot melt coating method, a curtain coating method or the like.
The thickness of the adhesive layer 13 is 10 μm to 100 μm, preferably 15 μm to 50 μm, and more preferably 25 μm to 45 μm from the viewpoint of adhesion after bonding.

剥離フィルム１４に形成する表面凹凸は、算術平均粗さＲ（ａ）＝３５０〜８５０ｎｍであり、４００〜８００ｎｍが好ましく、４５０〜７５０ｎｍがより好ましい。凹凸を形成する方法は、公知の方法を用いることができる。
なお、算術平均粗さＲ（ａ）とは、粗さ曲線から、その平均線の方向に基準長さ（下記式中Ｌの小文字）だけ抜き取り、この抜き取り部分の平均線から測定曲線までの偏差の絶対値を合計し、平均した値である。一つの傷が測定値に及ぼす影響が非常に小さくなり、安定した結果が得られるため、好ましい。

The adhesion layer 13 physically forms the surface asperity by bonding the peeling film 14 in which the asperity is formed and transferring the asperity. The surface asperity of the adhesive layer 13 having good adhesion properties is arithmetic average roughness R (a) = 300 nm to 800 nm, preferably 350 nm to 750 nm, and more preferably 400 nm to 700 nm.
As the peeling film 14, for example, a plastic film such as a polyester resin or a polyolefin resin, or a sealed paper such as cellophane or glassine paper can be used. Furthermore, a polyethylene terephthalate, polyethylene, polypropylene resin film or the like coated with a release agent such as a fluorine resin, a silicone resin, or a long chain alkyl group-containing carbamate on one side or both sides can be used.
The thickness of the release film varies depending on the material used, but is usually 10 to 250 μm, preferably 20 to 200 μm.

The surface asperities formed on the release film 14 have an arithmetic mean roughness R (a) of 350 to 850 nm, preferably 400 to 800 nm, and more preferably 450 to 750 nm. A well-known method can be used for the method of forming an unevenness | corrugation.
Arithmetic mean roughness R (a) is the deviation from the roughness curve to the measurement curve in the direction of the mean line by the reference length (lower case L in the following formula) The absolute values of are summed and averaged. It is preferable because one wound has a very small effect on the measured value and stable results can be obtained.

The adhesive layer of the present invention, which is limited as described above, is blended for a short time (10 to 120 minutes from immediately after peeling, preferably 20 to 90 minutes, particularly preferably) even after peeling from the limited release film (30 minutes to 60 minutes), can maintain the asperity shape and size, and then, after the attachment with the target adherend is started, this shape is easy also with the aid of applied pressure And adhere uniformly to the adherend. Another characteristic of this pasting is that when the release film without the surface roughness as described above is used, or when the adhesive layer from which the limited composition is used, the collapse of the uneven shape is quick. If it is too high or hardness is too high, the adhesion with the adherend is not uniform, and the ability to remove bubbles and water droplets is also impaired.
In the protective film having the pressure-sensitive adhesive layer of the present invention, at the time of bonding, while the pressure-sensitive adhesive layer concave portions in adjacent non-adhered parts are used one after another, defoaming progresses rapidly (pressure-sensitive adhesive surfaces from which bubbles are released are successively covered) I'm going to unite and stick with the clothes.
In addition, when such a bonding method is used, bubbles gradually develop even when it goes to long-term use after the completion of bonding, and the adherend on which this protective film is actually used Initial mechanical properties (chipping resistance, impact resistance) even when used for a long time without developing local physical defects due to bubbles or chemical defects including air (oxygen) with the adhesive layer Properties, initial heat resistance, initial weatherability, and initial peelability (without adhesive residue) are almost maintained, and a novel and innovative bonding method has been found. In addition, in the compounding body which requires longer time by the sticking characteristic, the tendency for the long-time holding | maintenance ability of an initial stage characteristic to be inferior is seen.

  The laminate of the present application has high adhesion properties to an adherend such as a car body by means of an adhesive layer. Furthermore, by controlling the surface roughness of the adhesive surface, the sticking characteristics (water and air bubbles) of the adherend are remarkably improved. Furthermore, since the adhesive layer is excellent in heat resistance and weather resistance, there is no adhesive residue even after peeling. In addition, since the adhesive surface of the adhesive layer is protected by the release film having high releasability until it is attached to the adherend, it can be distributed and transported without deteriorating the adhesiveness.

[Surface protective article]
A surface protection article according to a second embodiment of the present invention will be described. Examples of articles as adherends to which the laminate of the present application is attached include automobiles, aircraft, ships and the like. Coatings of various body parts of these articles, in particular car bodies (eg, front hood tips and other tip surfaces, rocker panels, etc.) exposed to dangers such as flying debris (eg sand, stones etc.), insects etc. It is effective for surface protection.
Furthermore, it can be used, for example, for windows, construction materials, digital signage, packaging, office supplies, and can be used in a wide range of fields such as electronics, security, and industry. Furthermore, it can be applied to waste packing, protection of medical device surfaces, and the like in the field of care and medical care.

  The results of evaluating the properties of the laminate are shown below.

Production Example 1: Preparation of Adhesive A
Acrylic adhesive A which is a copolymer comprising 40 to 55 parts by weight of butyl acrylate, 40 to 55 parts by weight of methyl acrylate, 1 to 15 parts by weight of vinyl acetate and 0.1 to 3 parts by weight of carboxyl group-containing acrylic oxide To the mixture were added 30 parts by weight of ethyl acetate, and the mixture was stirred at 23 ° C. for 30 minutes with a stirring blade to adjust the solid content to 23% by weight and the viscosity to 1000 CPS. The weight average molecular weight (Mw) of the adhesive A is 550,000, and the glass transition temperature is -16 ° C.

Preparation Example 2 Preparation of Adhesive B
30 parts by weight of ethyl acetate is added to acrylic adhesive B which is a copolymer containing 60 to 95 parts by weight of butyl acrylate, 5 to 35 parts by weight of ethyl acrylate and 0.1 to 5 parts by weight of carboxyl group-containing acrylic oxide The mixture was stirred at 23 ° C. for 30 minutes with a stirring blade to adjust the solid content to 23% by weight and the viscosity to 1000 CPS. The weight average molecular weight (Mw) of the adhesive B is 550,000, and the glass transition temperature is -46 ° C.

Example 1 Preparation of Laminate 1
Adhesive prepared by die-coating on a thermoplastic polyurethane film of thermoplastic polyurethane film (trade name: Argotec 49510, manufactured by Argotec, thickness 6 mil = 152.4 μm) laminated with a 50 μm polyethylene terephthalate protective film on one side A was applied and dried under conditions of 70 ° C. × 3 minutes to form a 30 μm-thick adhesive layer. Furthermore, a 75 μm thick polyethylene terephthalate film (Peeling film A, surface roughness 716 nm) peeled off with silicone resin is pressure bonded onto the adhesive layer surface using a rubber roller and cured for 1 day in an environment of 45 ° C. Then, a laminate 1 was obtained.

Example 2 Preparation of Laminate 2
Adhesive prepared by die-coating on a thermoplastic polyurethane film of thermoplastic polyurethane film (trade name: Argotec 49510, manufactured by Argotec, thickness 6 mil = 152.4 μm) laminated with a 50 μm polyethylene terephthalate protective film on one side A was applied and dried under conditions of 70 ° C. × 3 minutes to form a 30 μm-thick adhesive layer. Furthermore, a 75 μm thick polyethylene terephthalate film (Peeling film B, surface roughness 641 nm) peeled off with silicone resin is pressure bonded onto the adhesive layer surface using a rubber roller and cured for 1 day in an environment of 45 ° C. Then, a laminate 2 was obtained.

Comparative Example 1: Preparation of Laminate 3
Adhesive prepared by die-coating on a thermoplastic polyurethane film of thermoplastic polyurethane film (trade name: Argotec 49510, manufactured by Argotec, thickness 6 mil = 152.4 μm) laminated with a 50 μm polyethylene terephthalate protective film on one side B was applied and dried under conditions of 70 ° C. × 3 minutes to form a 30 μm-thick adhesive layer. Furthermore, a 75 μm thick polyethylene terephthalate film (release film A, surface roughness 700 nm) peeled off with silicone resin is pressure bonded onto the adhesive layer surface using a rubber roller and cured for 1 day in an environment of 45 ° C. The stack 3 was obtained.

Comparative Example 2: Laminate 4
As a comparative example, trade name: Scotchguard (laminated body 4) manufactured by 3M company was used.

[Comparative Example 3: Laminate 5]
A trade name NanoFusion Film (laminate 5) manufactured by CCL Industries was used as a comparative example.

[Test method]
(1) Adhesiveness The peeling film of the layered product cut into a size of width 25 mm and length 200 mm is peeled off, and it is on the coated board (width 50 mm, length 150 mm, thickness 1.2 mm) where the black paint for cars is applied. Then, using a 2 kg rubber roller, it was crimped for one reciprocation at a moving speed of 5 mm / sec. The adhesive strength of the laminate adhered to the coated plate after storage for 30 minutes in an environment of 23 ± 2 ° C. and 50 ± 5% RH was measured using a tensile tester (Strograph VG, manufactured by Toyo Seiki Seisakusho Co., Ltd.) The crosshead load was measured using a 100N crosshead speed 300 mm / min.
(2) Peeling force One of the peeling films of the laminate cut into a size of width 25 mm and length 200 mm is peeled off, and the peeling film is the upper cross of a tensile tester (Strograph VG, manufactured by Toyo Seiki Seisakusho Co., Ltd.) The film was fixed to the head, the other from which the release film was peeled off was fixed to the lower cross head, and the peel force between the adhesive layer and the release film was measured under conditions of cross head load 100 N and cross head speed 300 mm / min.
(3) Surface Roughness The release film is peeled off from the laminate, and the arithmetic mean roughness R (a) of the adhesive layer surface is measured using a three-dimensional light interference roughness meter (Contour GT, manufactured by Bruker AX). did.
(4) Bonding characteristics Peel off the peeling film of the laminate cut to a size of 40 mm in width and 130 mm in length, and mix 2-3 drops of baby shampoo (baby full-body shampoo, manufactured by Johnson & End Johnson) in 1 L of water The sprayed aqueous solution is sprayed onto the adhesive layer side, the surface, and a painted plate (width 50 mm, length 150 mm, thickness 1.2 mm) coated with black paint for automobiles, and the adhesive layer side of the laminate is made of rubber squeegee Then, it stuck on a paint board, pushing out bubbles and bubbles. Thereafter, it was left at room temperature, and the time until the bubbles and bubbles remaining on the adhesive layer surface and the coated plate were visually observed was measured.
(5) Heat resistance The peeling film of the laminate cut into a size of 40 mm wide and 130 mm long was peeled off, and 1 to 2 liters of water was mixed with 2-3 drops of baby shampoo (baby full-body shampoo, manufactured by Johnson & Johnson). The aqueous solution is sprayed onto the adhesive layer side, the surface, and a painted plate (width 50 mm, length 150 mm, thickness 1.2 mm) coated with black paint for automobiles, and the adhesive layer side of the laminate is squeegee made of rubber It stuck on a paint board, pushing out bubbles, bubbles, and water bubbles. Thereafter, the laminate was left to stand at room temperature for 1 day, heated in an oven set at 80 ° C. for 24 hours, and the laminate attached to the coated plate was peeled off, and the state of the coated plate was visually observed. This condition corresponds to one month of outdoor exposure in summer. Furthermore, it is confirmed that this test result also corresponds to the result of the working test in the car.
(6) Weatherability Accelerated weathering test: Irradiance received on one side of a laminate (150 mm long and 50 mm wide) affixed to a coating film using a SW type accelerated weathering tester specified in JIS B 7753: wavelength 300 to Accelerated weathering test which becomes 255 ± 45 W / m ² for 700 nm Sunshine super long life weather meter manufactured by Suga Test Instruments Co., Ltd. Model WEL-SUN-HC-B type In addition, the test condition of the above-mentioned accelerated weathering test is the following It is street.
-Number of sunshine carbon arc lamps: 4 lamps-Glass filter (A type) used-Power supply voltage: single phase AC 180 to 230 V
・ Condition at the time of irradiation Average discharge voltage current: 50V (± 2%), 60A (± 2%)
Temperature indicated by black panel thermometer: 63 ± 3%
Relative humidity: (50 ± 5)%
・ Rainfall conditions 12 minutes in 60 minutes first run (with deionized water)
・ Irradiance received by the surface of the test piece: 255 ± 45 W / m ^{2 for} 300 to 700 nm
Irradiation time: 1000 hours (equivalent to one year of outdoor exposure. Furthermore, the test results confirm that they also correspond to the results of practical tests in automobiles.)

実施例２では、実施例１で用いた剥離フィルムＡとは異なる表面粗さを有する剥離フィルムＢを用いて、粘着層の凹凸を形成した。比較例１では、実施例１で用いた粘着剤Ａとは異なる粘着剤Ｂを用いて、粘着層を形成した。表２および図２に示すように、粘着面の表面粗さが３５０〜７５０ｎｍの領域において、高い貼り付け特性を発現することができる。
さらに表２に示すように、実施例１、２と、比較例１〜３を比べると、実施例１、２の粘着層の耐熱性および耐候性は高く、試験後に被着体に対して糊残りなく容易に引き剥がすことができるのに対して、比較例１〜３の粘着層では、試験後に糊残りが観察された。

In Example 2, the unevenness of the adhesive layer was formed using Release Film B having a surface roughness different from that of Release Film A used in Example 1. In Comparative Example 1, a pressure-sensitive adhesive B different from the pressure-sensitive adhesive A used in Example 1 was used to form a pressure-sensitive adhesive layer. As shown in Table 2 and FIG. 2, in the area | region where the surface roughness of an adhesive surface is 350-750 nm, a high bonding characteristic can be expressed.
Furthermore, as shown in Table 2, when Examples 1 and 2 and Comparative Examples 1 to 3 are compared, the heat resistance and the weather resistance of the adhesive layers of Examples 1 and 2 are high, and the glue for the adherend after the test In the adhesive layers of Comparative Examples 1 to 3, the adhesive residue was observed after the test, while the adhesive layers of Comparative Examples 1 to 3 were able to be easily peeled off without remaining.

The evaluation results of the adhesive residue of the adhesive layer are shown below.
Example 1
A polyurethane film with a thickness of 150 μm was used as the base film, and a polyethylene terephthalate film with a thickness of 75 μm coated with a silicone resin was used as a release film. As the adhesive layer, adhesive layer A (Butyl acrylate as main monomer, copolymer of carboxyl group-containing monomers such as methyl acrylate and vinyl acetate, and copolymer of weight average molecular weight (Mw) of 1 to 1,000,000) ) Was applied using a knife coating method so that the applied amount after drying was 30 μm.

Comparative Example 4
A polyurethane film with a thickness of 150 μm was used as the base film, and a polyethylene terephthalate film with a thickness of 75 μm coated with a silicone resin was used as a release film. As the adhesive layer, adhesive layer B (A copolymer containing butyl acrylate as a main monomer, a copolymer of methyl methacrylate copolymerized with a weight average molecular weight (Mw) of 1 to 1,000,000) after drying is 30 μm It apply | coated and created using the knife coat method so that it might become.

[Evaluation items and evaluation method]
An automotive two-component polyurethane topcoat is sprayed onto a plate of polyolefin thermoplastic elastomer coated with an electrodeposition primer and an intermediate coat to a thickness of about 1 μm, dried at 60 ° C. for 10 minutes, and 30 at room temperature. After standing for a minute, the adhesive films prepared in Example 1 and Comparative Example 4 were attached to the coating. The surface state of the coated film was observed visually and with an optical microscope when the film attached to the coated surface was peeled off after standing for 168 hours in a thermostat at 80 ° C., and evaluated according to the following criteria.
(1) Adhesive residue ○: no adhesive residue on the coated surface △: slightly adhesive residue on the coated surface ×: adhesive residue on the front surface

DESCRIPTION OF SYMBOLS 10 laminated body 11 base film 13 adhesion layer 14 peeling film s1 surface

Claims (5)

A laminate for a surface protection film,
A substrate film formed of a thermoplastic resin;
Comprising a; a first adhesive layer formed on the surface side of the substrate film
The surface roughness of the adhesive layer is 350 to 750 nm,
The glass transition temperature of the adhesive layer, Ri -40～0 ° C. der,
The adhesive forming the adhesive layer is 40 to 55 parts by weight of butyl acrylate, 40 to 55 parts by weight of methyl acrylate, 1 to 15 parts by weight of vinyl acetate, and 0.1 to 3 parts by weight of carboxyl group-containing acrylic oxide An acrylic adhesive which is a copolymer containing
Stack. It comprises a release film provided on the side of the adhesive layer opposite to the substrate film ,
The surface roughness of the surface of the release film to the adhesive layer is 350 to 800 nm.
The laminate according to claim 1. In the release film, at least one release agent selected from a fluorine-based resin, a silicone resin, and a long chain-containing carbamate is applied to the surface with respect to the adhesive layer.
The laminated body of Claim 2 . A laminate according to claim 1;
Comprises; the laminate and the article was adhered to a surface by said adhesive layer
Surface protection article. It is a manufacturing method of the layered product for surface protection films, and
Providing a substrate film formed of a thermoplastic resin;
The first surface side of the base film, an adhesive layer, and the base film and the step of roughness on the opposite side of the surface to form an adhesive layer is 350～750Nm; equipped with,
The glass transition temperature of the adhesive layer, Ri -40～0 ° C. der,
The adhesive forming the adhesive layer is 40 to 55 parts by weight of butyl acrylate, 40 to 55 parts by weight of methyl acrylate, 1 to 15 parts by weight of vinyl acetate, and 0.1 to 3 parts by weight of carboxyl group-containing acrylic oxide An acrylic adhesive which is a copolymer containing
Method of manufacturing a laminate.

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