JP6690153B2 - Method for manufacturing laminated body - Google Patents

Description

  The present invention relates to a method for manufacturing a laminated body including a hot pressing step.

  As a method for manufacturing a laminated body such as a multilayer wiring board in which a plurality of functional layers are laminated, for example, various functional layers are laminated in order, and the laminated body is placed on a heat press machine and heated from above and below in the laminating direction. And a method of increasing the interlayer adhesion of each functional layer by applying pressure (hereinafter referred to as hot pressing or hot pressing) (for example, Patent Document 1). Due to the heat and pressure conditions at this time, the outermost layer of the laminate and the upper and lower press plates are bonded and the laminate is damaged, or in order to prevent the wiring or the element arranged on the outermost layer from being damaged, Usually, a support layer such as a release sheet is arranged between the lower press plate of the heat press machine and the laminate, and a protective film is arranged between the upper press plate and the laminate.

JP, 2014-220544, A

In the production of a laminate by hot pressing, the functional layer, which is the outermost layer of the laminate, is usually placed on the support layer without an adhesive layer or the like. This is to prevent the laminate from being contaminated due to outgas and adhesive residue due to the pressure-sensitive adhesive on the support layer when the laminate is taken out of the hot press machine after the hot pressing and the support layer is peeled off. However, when arranging the functional layer without interposing an adhesive layer or the like, since the lowermost functional layer in contact with the supporting layer is not fixed to the supporting layer, it is possible to stack another functional layer on the lowermost functional layer. However, there is a problem in that the stacking position of each functional layer and the stacking position of the stacked body with respect to the support layer during hot pressing cause misalignment.
When cutting the laminated body after hot pressing into a desired shape and size, after peeling the supporting layer from the laminated body, the laminated body is separately placed on another supporting layer via a dicing tape or the like. It is necessary to fix it to and cut it. Similarly, in the case of subjecting the laminated body after hot pressing to chemical treatment or the like, it is necessary to separately dispose the protective layer on the laminated body after peeling the support layer from the laminated body. Therefore, in the production of a laminate, a series of steps from lamination of functional layers to post-treatment after hot pressing cannot be carried out in a state of being fixed on a single support layer, which complicates the production process. There is a problem.

  The present invention has been made in view of the above problems, in a method for manufacturing a laminate including a hot pressing step, without contaminating the laminate, a series of steps from lamination of the functional layer to post-treatment, The main object of the present invention is to provide a method for producing a laminate, which can be carried out easily while being fixed on a single adhesive substrate.

  In order to solve the above problems, the present invention provides a preparation step of preparing an adhesive base material having a base material and an adhesive layer formed on one surface of the base material, and the adhesion of the adhesive base material. Laminating step of laminating a plurality of functional layers on a layer to form a laminate with an adhesive base material, heat pressing step of heating and pressing the laminate with an adhesive base material, with the adhesive base material A peeling step of peeling the adhesive base material from the laminate is provided.

According to the above invention, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive substrate has heat resistance capable of withstanding the hot-pressing conditions in the hot-pressing step, so that the laminate is fixed on the pressure-sensitive adhesive layer by hot-pressing. You can Further, by showing the removability of the adhesive layer, when peeling the adhesive substrate from the laminate after the hot pressing step, it becomes possible to peel without adhesive residue on the laminate side, It is possible to prevent contamination of the laminate. Furthermore, in the case of carrying out any step after the hot pressing step, by making the above-mentioned adhesive substrate function as a protective layer for protecting the laminate from a chemical solution or the like, or as a support layer when cutting the laminate. It is possible to perform any step after the hot pressing step while the laminate is fixed on the adhesive base material.
Thus, in the method for producing a laminate including the hot pressing step, the contamination of the laminate was suppressed, and a series of steps from lamination of the functional layer to post-treatment was fixed on a single adhesive substrate. It can be performed easily in the state.

  In the above-mentioned invention, it is preferred that the above-mentioned adhesive layer shows slight adhesiveness. Further, in the above invention, it is preferable that the adhesive layer is peeled off by irradiation with energy rays. By using these types of adhesive layers, it is possible to accurately determine the stacking position of the functional layer during the stacking process, and to sufficiently fix the stack, and in the peeling process, there is no adhesive residue on the stack side. This is because it is possible to easily peel off the adhesive base material without causing it.

  In the above invention, a cutting step of cutting the pressure-sensitive adhesive substrate-attached laminate may be provided between the hot pressing step and the peeling step. The functional layer is laminated on the adhesive layer of the adhesive substrate, the interlayer adhesion of each functional layer is increased by hot pressing, and the laminated body after hot pressing is accurately cut into a desired shape, and the adhesive substrate is peeled off. This is because the series of steps can be performed while being fixed on a single adhesive substrate, and the steps can be simplified.

  In the above invention, a chemical treatment step may be provided between the hot pressing step and the peeling step. By performing chemical treatment on the laminated body after the hot pressing process while it is fixed to the adhesive base material, the adhesive base material functions as a protective layer and prevents erosion and contamination of the laminated body by the chemical liquid. Because you can do it. Further, after the chemical treatment, since it is possible to easily peel off the adhesive substrate without adhesive residue on the laminate side, a series of steps from the laminating step to the peeling step including the chemical treatment step. This can be performed in a state of being fixed on a single adhesive substrate, and the process can be simplified.

  In the present invention, a series of steps from lamination of the functional layer to post-treatment can be carried out in a state of being fixed on a single adhesive substrate without contaminating the laminate, which is a simple step. An effect that a laminated body can be manufactured is exhibited.

It is process drawing which shows an example of the manufacturing method of the laminated body of this invention. It is a schematic sectional drawing which shows an example of the aspect of the laminated body with an adhesive base material. It is process drawing which shows a part of other example of the manufacturing method of the laminated body of this invention.

  Hereinafter, the method for manufacturing the laminate of the present invention will be described. The method for producing a laminate of the present invention comprises a preparatory step of preparing an adhesive base material having a base material and an adhesive layer formed on one surface of the base material, and the adhesive layer of the adhesive base material. Laminating step of laminating a plurality of functional layers to form a laminate with an adhesive substrate, a heat pressing step of heating and pressing the laminate with an adhesive substrate, the laminate with an adhesive substrate And a peeling step of peeling the adhesive base material.

A method for manufacturing a laminated body of the present invention will be described with reference to the drawings. FIG. 1 is a process drawing showing an example of a method for manufacturing a laminate of the present invention.
First, the adhesive base material 20 having the base material 11 and the adhesive layer 12 formed on one surface thereof is prepared (FIG. 1A, preparation step). Next, the plurality of functional layers 1a to 1c are laminated on the adhesive layer 12 of the adhesive base material 20 to form a laminated body 30 with an adhesive base material (FIG. 1 (b), laminating step). In addition, the laminated body formed from the plurality of functional layers 1a to 1c formed on the adhesive layer 12 in this step is referred to as a laminated body 10 'before hot pressing.
Next, the laminate 30 with the adhesive substrate is placed between the hot press plates 41 and 42. The protective film 13 is arranged on the side of the laminated body 30 with the adhesive substrate on which the adhesive substrate 20 is not arranged. The laminated body 10 can be obtained by hot pressing the laminated body 30 with the adhesive base material in the laminating direction (FIG. 1C, hot pressing step) and then peeling off the adhesive base material 20 ( FIG. 1D, peeling step).

According to the present invention, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive substrate has heat resistance capable of withstanding the hot-pressing conditions in the hot-pressing step, so that the laminate is fixed on the pressure-sensitive adhesive layer by hot pressing. You can Further, by showing the removability of the adhesive layer, when peeling the adhesive substrate from the laminate after the hot pressing step, it becomes possible to peel without adhesive residue on the laminate side, It is possible to prevent contamination of the laminate. Furthermore, in the case of carrying out any step after the hot pressing step, by making the above-mentioned adhesive substrate function as a protective layer for protecting the laminate from a chemical solution or the like, or as a support layer when cutting the laminate. It is possible to perform any step after the hot pressing step while the laminate is fixed on the adhesive base material.
Thus, in the method for producing a laminate including the hot pressing step, the contamination of the laminate was suppressed, and a series of steps from lamination of the functional layer to post-treatment was fixed on a single adhesive substrate. It can be performed easily in the state.

  Hereinafter, the method for producing a laminate of the present invention will be described step by step.

A. Preparation Step The preparation step in the present invention is a step of preparing an adhesive substrate having a substrate and an adhesive layer formed on one surface of the substrate.

1. Adhesive Layer The adhesive layer has heat resistance that can withstand the heat and pressure conditions in the hot pressing step described below, and exhibits removability that allows the adhesive substrate to be easily peeled in the peeling step.
The adhesive layer shows removability means that the functional layer directly formed on the adhesive layer can be adhered or adhered, the laminate is not destroyed in the peeling step, and adhesive residue is generated on the laminate side. It means that peeling is possible by suppressing the above.

Further, the pressure-sensitive adhesive layer exhibits heat resistance capable of withstanding hot-pressing conditions in the heat-pressing step means that the pressure-sensitive adhesive layer is a laminate fixed on the pressure-sensitive adhesive layer in various steps up to the peeling step including the heat-pressing step. The adhesiveness can be maintained to such an extent that it does not peel off, and when peeling the laminate in the peeling step, there is almost no contamination due to adhesive residue on the laminate and peeling can be easily performed. Refers to.
The heat resistance of the pressure-sensitive adhesive layer specifically means that the weight reduction rate of the pressure-sensitive adhesive layer is in the range of 1% to 10%, preferably less than 2.5%. The weight reduction rate is a value calculated by measuring the pressure-sensitive adhesive layer alone using a thermogravimetric-differential heating device (TG-DTA), and specifically, in a nitrogen atmosphere (gas flow rate: 150 ml / min). Then, the amount of change in weight when the temperature was raised from 30 ° C. to 250 ° C. at a heating rate of 10 ° C./min, and the weight reduction rate was calculated from the following formula. The weight (W1) of the adhesive layer at 30 ° C. and the weight (W2) of the adhesive layer at 250 ° C. were measured and calculated from the following formula.
Weight reduction rate (%) = [(W1 (g) −W2 (g)) / W1 (g)] × 100
The presence or absence of adhesive residue on the surface of the laminated body after peeling the adhesive substrate can be confirmed by observing the surface of the laminated body after peeling with an IR measurement or an optical microscope.

The pressure-sensitive adhesive layer preferably exhibits low outgassing properties under the hot pressing conditions in the hot pressing step. Specifically, the amount of outgas generated when the pressure-sensitive adhesive layer is heated at 200 ° C. for 0.5 hours is preferably 15 μg / cm ² or less, more preferably 10 μg / cm ² or less, and particularly 5 μg / cm ² or less. It is preferable. This is because the surface layer of the laminated body may be contaminated due to the generation of outgas, and a defect may occur during the subsequent process. This is because, for example, in the case of silicone or the like, the generated outgas influences the electrical characteristics or causes cissing or the like in the subsequent process, which causes a problem in the process.
The outgas generation amount is a value measured and calculated by the following method as a measurement sample by cutting the adhesive base material of the present invention using a polyimide film as a base material into a size of width 10 mm and length 10 mm. . Since the amount of outgas generated from the polyimide film alone under the same conditions is less than 0.3 μg / cm ^2, which is a negligible amount, the amount of outgas generated in the above measurement sample is defined as the amount of outgas generated in the adhesive layer.

(Measurement method and calculation method)
The measurement sample was heated at 200 ° C. for 0.5 hours by a purge & trap headspace sampler to trap the generated gas (outgas), and then the trapped components were separated and measured by a gas chromatograph mass spectrometer. .
The amount of gas generated was converted to a value per unit area of the adhesive layer as a conversion value based on the n-hexadecane standard, and the amount of outgas generated in the adhesive layer (outgas generated when heated at 200 ° C. for 0.5 hours) Amount and unit: μg / cm ² ).

Examples of such an adhesive layer include an adhesive layer exhibiting slight adhesiveness (first mode of the adhesive layer) and an adhesive layer peeled by irradiation with energy rays (second mode of the adhesive layer). By using these adhesive layers, the stacking position of the functional layer can be accurately determined during the stacking process, and the stack can be sufficiently fixed. In addition, the adhesive base material can be easily peeled off without leaving an adhesive residue on the laminate side in the peeling step.
Hereinafter, the adhesive layer will be described for each mode.

(1) First Aspect of Adhesive Layer The adhesive layer of the present aspect exhibits slight adhesiveness.
The pressure-sensitive adhesive layer of the present embodiment can sufficiently fix the laminate in a series of steps due to its initial adhesive force, and since the initial adhesive force is low, adhesive residue is generated on the laminate side in the peeling step. Can be suppressed and the adhesive substrate can be easily peeled off.

Here, the slight adhesiveness of the pressure-sensitive adhesive layer of the present embodiment means that the laminate can be fixed before and after hot pressing, and that the adhesive strength is such that no adhesive residue is left on the laminate during peeling. . Specifically, the initial adhesive force of the adhesive layer of this embodiment is 6 N / 25 mm or less, preferably 3 N / 25 mm or less, and more preferably 2 N / 25 mm or less. Further, the initial adhesive strength of the adhesive layer of this aspect is preferably 0.05 N / 25 mm or more.
The adhesive strength is such that a polyimide film (thickness 25 μm, manufactured by Toray DuPont, product name: 100H) is used as a base material, and the adhesive layer of the present embodiment is on one side of the base material within the thickness range described later. A strip-shaped test piece having a width of 25 mm and a length of 150 mm was cut using the adhesive base material formed in No. 2, and then laminated on a stainless steel plate under the conditions according to the JIS Z0237 standard, and finally, the test was performed. It can be measured by peeling the piece in the length direction of the test piece under the conditions of a peeling angle of 180 °, a peeling speed of 300 mm / min and room temperature. Further, for such 180 ° peel strength measurement, for example, a universal testing machine 5565 manufactured by Instron can be used.

The composition of the pressure-sensitive adhesive layer of the present embodiment is not particularly limited as long as it is a composition capable of exhibiting the above-mentioned initial pressure-sensitive adhesive force, but among them, it is preferable to include at least an acrylic resin, and to include an acrylic resin and a cured resin. Is more preferable. Since the pressure-sensitive adhesive layer of the present embodiment contains the acrylic resin and the cured resin, the initial pressure-sensitive adhesive strength is low, and it is possible to exhibit high heat resistance capable of withstanding the heat and pressure conditions of the hot pressing step, and further low outgassing property. is there.
Here, that the pressure-sensitive adhesive layer of the present embodiment contains an acrylic resin, in the pressure-sensitive adhesive layer, the acrylic resin may be present alone without forming cross-linking, between acrylic resin or acrylic resin It may exist as a crosslinked body formed by cross-linking between the resin and another resin, and both the above simple substance and the above crosslinked body may exist.
Further, the curable resin contained in the adhesive layer of the present embodiment refers to a thermosetting resin or a photocurable resin that is cured by being irradiated with heat or light.

The pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of the present embodiment containing an acrylic resin and a cured resin may be one containing an acrylic resin and a curable resin, and one of the two embodiments described below can be used. It can be preferably used.
That is, 1st aspect of the adhesive composition used for formation of the adhesive layer of this aspect contains an acrylic resin, an epoxy thermosetting resin, and a hardening | curing agent, and the said epoxy thermosetting resin is the said acrylic resin. It is contained in the range of 20 to 60 parts by weight with respect to 100 parts by weight.
Moreover, the 2nd aspect of the adhesive composition used for formation of the adhesive layer of this aspect contains an acrylic resin, a crosslinking agent, a photocurable resin, and a photoinitiator.

The pressure-sensitive adhesive layer of the present aspect is formed from the pressure-sensitive adhesive composition of each of the above-described aspects, thereby exhibiting a desired initial pressure-sensitive adhesive force, and the cohesive force of the pressure-sensitive adhesive layer is improved to accelerate the pressure-sensitive adhesive force. Can be suppressed and excellent releasability can be exhibited. For this reason, in the peeling step, it is possible to reduce the occurrence of adhesive residue on the laminate side and the load on the laminate due to adhesion, deformation, etc., and it becomes possible to easily peel the adhesive substrate. Further, since the adhesive layer formed by the adhesive composition of each of the above-described embodiments contains a cured resin obtained by curing an epoxy thermosetting resin or a photocurable resin, it has higher heat resistance than an acrylic resin alone. It can be shown and can exhibit higher low outgassing.
In addition, the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition of each of the above aspects can exhibit high chemical resistance, and even when performing a step using a chemical solution as an arbitrary step, the adhesive force due to the chemical Can be prevented and peeling of the laminate from the adhesive substrate can be prevented.
Hereinafter, the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of this embodiment will be described for each mode.

(A) First Aspect of Adhesive Composition The adhesive composition of the present aspect contains an acrylic resin, an epoxy thermosetting resin, and a curing agent, and the epoxy thermosetting resin is 100 weight% of the acrylic resin. It is contained within the range of 20 parts by weight to 60 parts by weight with respect to parts.
The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present embodiment contains a simple substance of an acrylic resin and an epoxy curable resin. It may also include a crosslinked product of an acrylic resin or a crosslinked product of a reaction between an acrylic resin and an epoxy thermosetting resin.

(i) Acrylic Resin The acrylic resin is not particularly limited, and includes, for example, a (meth) acrylic acid ester polymer obtained by homopolymerizing a (meth) acrylic acid ester, and a (meth) acrylic acid ester as a main component ( An example is a (meth) acrylic acid ester copolymer obtained by copolymerizing a (meth) acrylic acid ester with another monomer. Of these, a (meth) acrylic acid ester copolymer is preferable.
Here, in the (meth) acrylic acid ester copolymer, the main component being (meth) acrylic acid ester means that the ratio of the (meth) acrylic acid ester in the copolymer (copolymerization ratio) is more than 30% by mass. A large amount means that the copolymerization ratio is preferably 51% by mass or more.
In addition, in this specification, (meth) acrylic acid shall mean at least one of acrylic acid and methacrylic acid.

As the (meth) acrylic acid ester, a (meth) acrylic acid alkyl ester such as a linear or branched alkyl ester having 1 to 30 carbon atoms and a (meth) acrylic acid cycloalkyl ester can be used. Specific examples of the (meth) acrylic acid alkyl ester include those disclosed in JP-A-2014-101457 and the like. The (meth) acrylic acid ester may contain 1 type (s) or 2 or more types.
Of these, (meth) acrylic acid esters having 1 to 18 carbon atoms, particularly 1 to 8 carbon atoms are preferable. This is because the glass transition point (° C.) of the acrylic resin can be set within the range described below, and the adhesiveness and heat resistance of the adhesive layer are improved.

The acrylic resin may be a copolymer of (meth) acrylic acid ester and a monomer or oligomer. In addition to the (meth) acrylic acid ester, if necessary, other monomers or oligomers may be included as copolymerization components to improve cohesive force, heat resistance, and the like. Examples of the copolymerization component include a functional group-containing (meth) acrylate copolymerizable with a (meth) acrylic acid ester. Specifically, carboxyl group-containing monomers, acid anhydride group-containing monomers, hydroxyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, epoxy group-containing monomers, vinyl esters, vinyl ethers, aromatic vinyl compounds Etc.
Further, as the copolymerization component, a nitrogen-containing monomer such as a cyano group-containing monomer, an amide group-containing monomer, an amino group-containing monomer or an isocyanate group-containing monomer may be used.
The above copolymerization component may be contained in the acrylic ester polymer as a copolymerization component.

The mass average molecular weight of the acrylic resin is preferably in the range of 100,000 to 2,000,000, more preferably in the range of 200,000 to 1,000,000. When the mass average molecular weight is smaller than the above range, the adhesive strength of the adhesive layer may be poor, while when it is larger than the above range, the coatability of the adhesive composition is deteriorated, and an epoxy thermosetting resin is used. In some cases, it becomes difficult to obtain the desired adhesiveness in the adhesive layer due to the reduced compatibility of the.
In addition, in this specification, a mass average molecular weight is a polystyrene conversion value at the time of measuring by gel permeation chromatography (GPC), for example, Tosoh Corporation HLC-8220GPC is used as a measuring device, and Tosoh is used as a column. TSKGEL-SUPERMULTIPORE-HZ-M manufactured by Co., Ltd. can be measured by using THF as a solvent and standard polystyrene having a molecular weight of 1050, 5970, 18100, 37900, 96400, 706000 as a standard product.

The acrylic resin preferably has a glass transition point of -20 ° C or higher and 30 ° C or lower, and particularly preferably in the range of -15 ° C to 20 ° C. By using an acrylic resin having a glass transition point in the above range as the main component of the pressure-sensitive adhesive composition, it is possible to improve the compatibility between the acrylic resin and other components while maintaining the cohesive force. .
The glass transition point of the acrylic resin can be appropriately adjusted by changing the type of monomer units used, the ratio of monomer units to be combined, and the like. Some acrylic resins have a glass transition point within the above range even in the case of a polymer (homopolymer) obtained by homopolymerizing monomers, but the glass transition point of the homopolymer is not within the above range. The use of the monomer unit is not limited, and the glass transition point of the copolymer obtained by combining various monomer units in combination may be within the above range.
In the present specification, the glass transition point means a value measured by a method (DMA method) based on a peak top value of loss tangent (tan δ). The loss tangent is determined by the value of loss elastic modulus / storage elastic modulus. These elastic moduli are measured by using a dynamic viscoelasticity measuring device for the stress when a force is applied to the polymer or copolymer at a constant frequency.

  The acrylic resin can be obtained by polymerizing the above-mentioned (meth) acrylic acid ester, monomers such as monomers and oligomers by a method such as ordinary solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization. .

(ii) Epoxy Thermosetting Resin The epoxy thermosetting resin has at least one epoxy group or glycidyl group. The epoxy thermosetting resin is cured by a cross-linking polymerization reaction when used in combination with a curing agent which will be described later to become an epoxy curable resin.

The epoxy thermosetting resin has an epoxy equivalent of 100 g / eq. ~ 2000 g / eq. It is preferably within the range. If the epoxy equivalent of the epoxy thermosetting resin is less than the above range, the crosslink density during curing may be too high and the adhesive strength of the adhesive layer may decrease from the desired range, while if it exceeds the above range. However, the heat resistance of the adhesive layer may be insufficient.
The epoxy equivalent is the number of grams of the resin containing 1 gram equivalent of epoxy group measured by the method according to JIS K7236.

  The mass average molecular weight of the epoxy thermosetting resin is not particularly limited, but it is generally preferably in the range of 300 to 5000 from the viewpoint of compatibility with the acrylic resin. From the viewpoint of the heat resistance of the adhesive layer, it is more preferable to use a high molecular weight epoxy thermosetting resin within the above range.

  Examples of the epoxy thermosetting resin include epoxy resins disclosed in JP2011-202045A. Among them, an epoxy resin having a rigid structure such as a biphenyl skeleton, a bisphenol skeleton, a stilbene skeleton in its main chain is preferable, a bisphenol type epoxy resin is more preferable, and a bisphenol A type epoxy resin is particularly preferable.

Among the epoxy thermosetting resins, bisphenol A type epoxy resins include those that are liquid at room temperature and those that are solid at room temperature, depending on the number of repeating units of the bisphenol skeleton. The bisphenol A type epoxy resin having 1 to 3 carbon atoms in the main chain is liquid at room temperature, and the bisphenol A type epoxy resin having 2 to 10 carbon atoms in the main chain is solid at room temperature. As the bisphenol A type epoxy resin which is solid at room temperature, those having a glass transition point in the range of 50 ° C. to 150 ° C. are preferable from the viewpoint of mechanical strength and heat resistance.
Examples of commercially available bisphenol A type epoxy resins having a main chain of 1 to 3 which are liquid at room temperature and bisphenol A type epoxy resins having a main chain of 2 to 10 which are solid at room temperature include, for example, JP-A-2011-202045. And those disclosed in.

  In order to form an adhesive layer having a low initial adhesive force, capable of maintaining the adhesive force under a hot-pressure environment, and having a small amount of adhesive residue, the epoxy thermosetting resin is 20 parts by weight per 100 parts by weight of an acrylic resin. It may be contained in the range of 60 parts by weight to 60 parts by weight, and preferably in the range of 30 parts by weight to 50 parts by weight. This is because if the blending amount of the epoxy thermosetting resin is less than the above range, the initial adhesive force of the adhesive layer tends to increase or the adhesive force tends to increase in a hot-pressing environment. On the other hand, when the compounding amount of the epoxy thermosetting resin exceeds the above range, the initial adhesive force may be lowered, and it may be difficult to bond the functional layers constituting the laminate at room temperature.

(Iii) Curing agent The epoxy thermosetting resin undergoes a reaction due to heating or the like to be cured, but normally, a curing agent for accelerating the curing reaction is contained in the pressure-sensitive adhesive composition.
The above-mentioned curing agent may be one that can react with the epoxy thermosetting resin in an equivalent amount, and for example, an amine-based curing agent, an acid anhydride-based curing agent, and a phenol-based curing agent can be preferably used. Examples of the curing agent that can cure (polymerize) the epoxy thermosetting resin independently include, for example, an imidazole curing agent and a cationic curing agent. Above all, it is preferable to use an imidazole-based curing agent or a cation-based curing agent that can expect performance derived from the skeleton of the epoxy thermosetting resin and that can cure the epoxy thermosetting resin independently even if the addition amount is small.

The compounding amount of the curing agent can be appropriately set according to the polymerization mode of the epoxy thermosetting resin. For example, when the epoxy thermosetting resin is polymerized and cured alone, the amount of the curing agent is preferably in the range of 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the epoxy thermosetting resin. . On the other hand, when the epoxy thermosetting resin and the curing agent are polymerized in an equivalent amount to cure the epoxy thermosetting resin, the compounding amount of the curing agent is 0.7 to 1.2 with respect to the epoxy equivalent of the epoxy thermosetting resin. It is preferable that
When the compounding amount of the curing agent with respect to the epoxy thermosetting resin is small, insufficient curing such as long curing time of the epoxy thermosetting resin when the pressure-sensitive adhesive composition is cured to form the adhesive layer. In some cases, it may be difficult to obtain the desired tackiness. On the other hand, when the compounding amount of the curing agent becomes excessive, the storage stability of the pressure-sensitive adhesive composition decreases, or the curing density of the epoxy thermosetting resin becomes too high, and the pressure-sensitive adhesive layer does not exhibit the desired pressure-sensitive adhesiveness. There is.

(Iv) Other Materials The pressure-sensitive adhesive composition of this embodiment may contain a crosslinking agent. In the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition of the present embodiment, the acrylic resin usually exists as a simple substance without forming cross-linking, but by adding a cross-linking agent to the pressure-sensitive adhesive composition, it can be obtained. The above-mentioned pressure-sensitive adhesive layer partially contains a cross-linked product formed by cross-linking between acrylic resins. This makes it possible to obtain an adhesive layer with improved stickiness while maintaining the adhesive strength. As the cross-linking agent, conventionally known ones can be used, and examples thereof include a polyfunctional epoxy compound and an isocyanate compound.

  Furthermore, the pressure-sensitive adhesive composition of the present embodiment may optionally contain a lubricant, a plasticizer, a filler, a filler, an antistatic agent, an antiblocking agent, a light stabilizer, a dye, a colorant such as a pigment, and the like. You may include the agent. Further, if necessary, a silane-based, titanium-based, aluminum-based coupling agent or the like can be included.

(B) Second Aspect of Adhesive Composition The adhesive composition of the present aspect contains an acrylic resin, a crosslinking agent, a photocurable resin, and a photoinitiator.
The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present embodiment contains at least a cured resin obtained by curing a crosslinked acrylic resin and a photocurable resin. The adhesive layer may contain a simple substance of acrylic resin together with a cross-linked body of acrylic resin.

The pressure-sensitive adhesive composition of the present embodiment, by containing a photocurable resin, at the time of forming the pressure-sensitive adhesive layer, the photocurable resin is cured in the coating layer of the pressure-sensitive adhesive composition by irradiation with energy rays to form a cured resin. Therefore, it is considered that the above-mentioned coating layer becomes moderately hard, and even if the crosslinking reaction of the acrylic resin proceeds, adhesive residue hardly occurs and the adhesive layer has excellent releasability.
The type of energy ray used for curing the photocurable resin can be the same as that described in the section “(2) Second mode of adhesive layer” described later.

(i) Acrylic resin The acrylic resin is not particularly limited and may be the same as the acrylic resin in the section "(a) First embodiment of pressure-sensitive adhesive composition", acrylic acid ester polymer or (meth) acrylic. A (meth) acrylic acid ester copolymer having an acid ester as a main component is used. Of these, a (meth) acrylic acid ester copolymer is preferable.
The weight average molecular weight of the acrylic resin is preferably within the range of 50,000 to 1,000,000, more preferably within the range of 100,000 to 800,000, from the viewpoint of tackiness and coatability.
The (meth) acrylic acid ester, the monomer and the oligomer in the acrylic resin, and the polymerization method thereof and the like can be the same as those described in the section “(a) First embodiment of pressure-sensitive adhesive composition”. .

  Regarding the glass transition point of the acrylic resin and the effect obtained by exhibiting the glass transition point, the glass transition point of the acrylic resin described in “(a) First embodiment of pressure-sensitive adhesive composition” and the effect thereof Can be similar to.

(ii) Photocurable resin As the photocurable resin, any radically polymerizable compound that can be polymerized by irradiation with a desired energy ray can be used without particular limitation, and examples thereof include an acrylate group, a vinyl group, and allyl. Group, a monomer, an oligomer, a prepolymer having a radically polymerizable unsaturated group such as an isopropenyl group. Examples of such compounds include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyethylene (meth) acrylate, silicone (meth) acrylate, polyol (meth) acrylate, and the like. The (meth) acrylate-based photocurable compound can be preferably used. You may use these individually or in combination of 2 or more types. Among them, a bifunctional monomer or oligomer can be preferably used.

  From the viewpoint of compatibility with acrylic resins, for example, epoxy (meth) acrylates obtained by introducing (meth) acrylic acid into an epoxy resin and urethane (meth) acrylates obtained by introducing (meth) acrylic acid into a urethane resin. Can be preferably used.

  The photocurable resin is preferably contained in the range of 5 to 60 parts by weight, and more preferably in the range of 5 to 40 parts by weight, based on 100 parts by weight of the acrylic resin. This is because by including the photocurable resin in the above range, it is possible to further improve the initial adhesive force of the adhesive layer, the cohesive force, and the change in the adhesive force when the adhesive layer is placed in a hot pressure environment.

(iii) Photoinitiator The photoinitiator is not particularly limited as long as it can exhibit a living radical polymerization initiation ability by irradiation with light and can cure a photocurable resin, and a known photoinitiator is used. Depending on the type of the photocurable resin, one kind or two or more kinds can be appropriately selected from the initiator. Specific examples include acetophenones, benzophenones, α-hydroxyketones, benzylmethyl ketals, α-aminoketones, and bisacylphosphine oxides.
When urethane acrylate is used as the photocurable resin, the photoinitiator is preferably a bisacylphosphine photoinitiator. The photoinitiator has heat resistance, and when applying the pressure-sensitive adhesive composition to the substrate and performing the light irradiation, the photocurable resin is surely applied even when the light irradiation is performed through the substrate. This is because it can be cured.

(iv) Cross-linking agent The cross-linking agent is only required to be able to cross-link the acrylic resin, and conventionally known cross-linking agents such as polyfunctional epoxy compounds and isocyanate compounds can be used. Specific examples thereof include polyfunctional epoxy compounds and isocyanate compounds disclosed in JP 2012-177084A.

  The cross-linking agent is preferably contained in the range of 0.1 parts by weight to 20 parts by weight, and more preferably in the range of 0.5 parts by weight to 10 parts by weight with respect to 100 parts by weight of the acrylic resin. This is because it is possible to enhance the cohesiveness while suppressing the initial adhesive force of the obtained adhesive layer, facilitate reattachment, and prevent the occurrence of floating and peeling during hot pressing.

  Furthermore, the pressure-sensitive adhesive composition of the present aspect can optionally contain any additive or coupling agent described in the section "(a) First aspect of pressure-sensitive adhesive composition".

(C) Method for preparing pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of each aspect can be prepared by mixing the above-mentioned components and kneading or dispersing as necessary. The kneading or dispersing method is not particularly limited, and a conventionally known kneading and dispersing machine disclosed in, for example, JP-A-2014-234460 can be applied.
Further, in the pressure-sensitive adhesive composition, each component may be mixed by adding a diluent solvent for adjusting the viscosity.

(D) Others The thickness of the pressure-sensitive adhesive layer of the present embodiment may be any size as long as it can exhibit a desired pressure-sensitive adhesive force, and is preferably in the range of 3 μm to 50 μm, and more preferably in the range of 5 μm to 30 μm.

(2) Second Aspect of Adhesive Layer The adhesive layer of the present aspect is peeled off by irradiation with energy rays. The pressure-sensitive adhesive layer of the present embodiment can sufficiently fix the laminate in a series of steps, and by irradiating with energy rays in the peeling step, the adhesive strength is reduced and the peelability is improved, Adhesive residue hardly occurs on the laminate side, and the adhesive base material can be easily peeled off.

Here, the peeling of the adhesive layer of the present embodiment by irradiation with energy rays means that the object can be fixed by exhibiting strong adhesiveness before being subjected to irradiation with energy rays, while if it is subjected to irradiation with energy rays, it becomes adhesive. It means that the material has physical properties such that the force is remarkably reduced and it can be easily peeled from the object. Specifically, the adhesive force of the adhesive layer of the present aspect before irradiation with energy rays is 0.5 N / 25 mm or more and 20 N / 25 mm or less, and the adhesive force of the adhesive layer of this aspect after irradiation with energy rays is 2.0 N. It is preferably / 25 mm or less.
For the adhesive strength, a polyester film (thickness: 50 μm) is used as a base material, and the adhesive base material is formed on one surface of the base material so that the adhesive layer of the present embodiment has a thickness within the range described below. It is measured by the same method as the method for measuring the adhesive force described in the section (1) First mode of adhesive layer.

  Examples of energy rays include light rays such as deep ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X rays and γ rays, and electron rays, proton rays, neutron rays, and the like. Among them, ultraviolet rays are preferable from the viewpoint of versatility and the like, and the ultraviolet rays preferably have a wavelength range of 150 nm to 450 nm.

  The composition of the pressure-sensitive adhesive layer of the present embodiment may be one that exhibits the above-mentioned pressure-sensitive adhesive force before and after irradiation with energy rays, for example, a composition containing at least a resin (adhesive main agent), an energy ray-polymerizable oligomer, and a polymerization initiator. be able to. With such a composition, the energy ray-polymerizable oligomer contained in the adhesive layer of the present embodiment is cured by irradiation with energy rays, and the adhesive strength can be reduced. Further, at this time, since the cohesive force is increased, transfer to the laminate is less likely to occur, and peeling of the pressure-sensitive adhesive layer of this embodiment is facilitated.

  Examples of the resin include acrylic resins, polyester resins, polyimide resins, silicone resins and the like, which are generally used as the main component of the pressure-sensitive adhesive. Among them, acrylic resins are preferred. This is because the heat resistance of the acrylic resin allows the pressure-sensitive adhesive layer of the present embodiment to exhibit high heat resistance and low outgassing that can sufficiently withstand the hot-pressing environment in the hot pressing step.

Therefore, a preferable composition of the pressure-sensitive adhesive layer of the present embodiment is one containing an acrylic resin, an energy ray-polymerizable oligomer, a polymerization initiator and a crosslinking agent.
In the pressure-sensitive adhesive layer of the present embodiment, the acrylic resin usually exists as a crosslinked product obtained by crosslinking between acrylic resins by the crosslinker, but a single acrylic resin may be contained together with the crosslinked product. Good.
Examples of the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of the present embodiment include those containing an acrylic resin, an energy ray-polymerizable oligomer, a polymerization initiator, and a crosslinking agent.

(A) Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer of the present embodiment preferably contains an acrylic resin, an energy ray-polymerizable oligomer, a polymerization initiator, and a crosslinking agent.
Hereinafter, each composition contained in the pressure-sensitive adhesive composition will be described.

(I) Acrylic resin The acrylic resin is not particularly limited, and includes, for example, a (meth) acrylic acid ester polymer obtained by homopolymerizing a (meth) acrylic acid ester, and a (meth) acrylic acid ester as a main component (meth). ) A (meth) acrylic acid ester copolymer obtained by copolymerizing an acrylic acid ester with another monomer can be mentioned. Of these, a (meth) acrylic acid ester copolymer is preferable.
Specific examples of the (meth) acrylic acid ester and other monomers include those disclosed in JP 2012-31316 A and the like. The other monomers may be used alone or in combination of two or more. In addition, the main component here means that the copolymerization ratio is 51% by mass or more, and preferably 65% by mass or more.

  Above all, as the acrylic resin, a (meth) acrylic acid ester copolymer obtained by copolymerizing a (meth) acrylic acid ester as a main component and a hydroxyl group-containing monomer copolymerizable with the (meth) acrylic acid ester Or a (meth) acrylic acid ester copolymer obtained by copolymerizing a (meth) acrylic acid ester as a main component with a hydroxyl group-containing monomer and a carboxyl group-containing monomer copolymerizable with the (meth) acrylic acid ester. It can be preferably used.

  The copolymerizable hydroxyl group-containing monomer and carboxyl group-containing monomer are not particularly limited, and for example, the hydroxyl group-containing monomer and carboxyl group-containing monomer disclosed in JP 2012-31316 A are used.

  The mass average molecular weight (Mw) of the acrylic resin is preferably in the range of 200,000 to 1,000,000, and more preferably in the range of 200,000 to 800,000. By setting the mass average molecular weight of the acrylic resin within the above range, it is possible to obtain an adhesive layer which can exhibit a sufficient initial adhesive force and can exhibit high heat resistance and low outgassing property in a hot pressure environment. Because you can.

  When the acrylic resin is a (meth) acrylic acid ester copolymer of a (meth) acrylic acid ester, a copolymerizable hydroxyl group-containing monomer and a carboxyl group-containing monomer, the hydroxyl group-containing monomer and the above The mass ratio with the carboxyl group-containing monomer is preferably in the range of 51:49 to 100: 0, and more preferably 75:25 to 100: 0. This is because if the weight ratio of each monomer is within the above range, effective reduction of the adhesive force due to irradiation with energy rays can be expected in the peeling step, and it is possible to suppress the occurrence of adhesive residue on the laminate side. Moreover, it is because high heat resistance can be exhibited under the hot pressing condition in the hot pressing step.

(Ii) Energy ray-polymerizable oligomer The energy ray-polymerizable oligomer is not particularly limited as long as it can be polymerized by irradiation with energy rays, and examples thereof include photoradical polymerizable, photocationic polymerizable, and photoanionic polymerizable. Oligomers. Of these, photo-radical polymerizable oligomers are preferable. This is because the curing rate is high, and it is possible to select from a wide variety of compounds, and further it is possible to easily control the physical properties such as the tackiness before curing and the releasability after curing.
Examples of the radical photopolymerizable oligomer include those disclosed in JP-A-2012-31316, and these may be used alone or in combination of two or more kinds.

  The mass average molecular weight (Mw) of the energy ray-polymerizable oligomer is not particularly limited, but is preferably in the range of 250 to 8000, and more preferably in the range of 250 to 5000. If the mass average molecular weight is within the above range, the adhesive layer of the present embodiment exhibits desired adhesiveness before irradiation with energy rays, and after irradiation with energy rays, generation of adhesive residue on the laminate side is suppressed, and easily. This is because it can be peeled off.

  The pressure-sensitive adhesive composition can control the adhesive force of the pressure-sensitive adhesive layer after irradiation with energy rays by adjusting the amount of the energy ray-polymerizable oligomer. The content of the energy ray-polymerizable oligomer in the pressure-sensitive adhesive composition is preferably 10 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 50 parts by weight, based on 100 parts by weight of the acrylic resin. Is preferred. When the content is within the above range, the crosslinking density of the pressure-sensitive adhesive layer of the present embodiment after irradiation with energy rays is sufficient, so that desired peelability can be realized. In addition, it is possible to suppress the generation of adhesive residue on the laminate side due to a decrease in the cohesive force of the pressure-sensitive adhesive composition.

(Iii) Polymerization initiator As the above-mentioned polymerization initiator, a general photopolymerization initiator can be used. Above all, the temperature is raised from 30 ° C to 190 ° C at a heating rate of 10 ° C / min to 190 ° C. A photopolymerization initiator having a weight reduction rate of 50% or less, particularly 20% or less when thermogravimetrically measured after being kept for 30 minutes is preferable. By selecting such a photopolymerization initiator, even if the pressure-sensitive adhesive layer of the present embodiment is exposed to the hot-pressing condition in the hot pressing step, it is possible to prevent the decrease in the pressure-sensitive adhesive force.
The weight reduction rate can be determined by measuring the weight using a commercially available thermogravimetric measuring device, for example, DTG-60A manufactured by Shimadzu Corporation. Specifically, the above polymerization initiator is analyzed (atmosphere gas: nitrogen, gas flow rate: 50 ml / min, temperature range: 30 ° C. to 190 ° C., temperature raising condition: 10 ° C./min), and the polymerization start at 30 ° C. The weight (W1) of the agent and the weight (W2) of the above-mentioned polymerization initiator after reaching 190 ° C. for 30 minutes are measured and calculated from the following formula.
Weight reduction rate (%) = [(W1 (g) −W2 (g)) / W1 (g)] × 100

  Examples of commercially available products of such a polymerization initiator include IRGACURE754, IRGACURE2959, and IRGACURE819 (all manufactured by BASF Japan Ltd.).

The content of the polymerization initiator in the pressure-sensitive adhesive composition is within the range of 0.01 parts by weight to 10 parts by weight with respect to 100 parts by weight of the total of the acrylic resin and the energy ray-polymerizable oligomer, and among them, 0.5 It is preferably within the range of 3 to 3 parts by weight. If the content of the polymerization initiator is less than the above range, the polymerization reaction of the energy ray-polymerizable oligomer does not sufficiently occur, the adhesive force of the adhesive layer of this aspect after irradiation with energy rays becomes excessively high, and peeling property is realized. Sometimes you can't. On the other hand, when the content exceeds the above range, the energy rays can reach only in the vicinity of the energy ray irradiation surface, the curing of the pressure-sensitive adhesive layer of the present embodiment becomes insufficient, or the cohesive force of the pressure-sensitive adhesive composition decreases. However, it may cause the adhesive residue.
When the pressure-sensitive adhesive composition contains an energy ray-polymerizable oligomer and an energy ray-polymerizable monomer described below, the total amount of the acrylic resin, the energy ray-polymerizable oligomer, and the energy ray-polymerizable monomer is 100 parts by weight. On the other hand, the content of the polymerization initiator is preferably within the above range.

(Iv) Cross-linking agent The cross-linking agent is not particularly limited as long as it cross-links at least acrylic resins, and examples thereof include an isocyanate cross-linking agent and an epoxy cross-linking agent. Specific examples of the isocyanate-based cross-linking agent and the epoxy-based cross-linking agent include those disclosed in JP 2012-31316 A.
The above-mentioned cross-linking agents can be used alone or in combination of two or more, and can be appropriately selected depending on the type of acrylic resin.

The content of the cross-linking agent in the pressure-sensitive adhesive composition can be appropriately set according to the type of the cross-linking agent, but is, for example, in the range of 0.01 to 15 parts by weight with respect to 100 parts by weight of the acrylic resin. In particular, the range of 0.01 to 10 parts by weight is preferable.
If the content of the cross-linking agent is less than the above range, the adhesion between the pressure-sensitive adhesive layer of the present embodiment and the laminate is poor, and when the positional deviation of the laminate occurs during hot pressing, or when the laminate is peeled off, the present embodiment The adhesive layer may cause cohesive failure, leaving adhesive residue on the laminate side. On the other hand, when the content of the cross-linking agent exceeds the above range, the cross-linking agent remains as an unreacted monomer in the pressure-sensitive adhesive layer of the present embodiment after irradiation with energy rays, which causes the generation of adhesive residue due to a decrease in cohesive force. There are cases.

(V) Optional Composition The pressure-sensitive adhesive composition may contain an energy ray-polymerizable monomer in addition to the energy ray-polymerizable oligomer described above. When the pressure-sensitive adhesive layer of this embodiment is irradiated with energy rays, the pressure-sensitive adhesive composition is cured by three-dimensional crosslinking to reduce the pressure-sensitive adhesive force, and the cohesive force of the pressure-sensitive adhesive composition is increased so that the pressure-sensitive adhesive composition is not transferred to the laminate side. Because it can be
As the energy ray-polymerizable monomer, a photoradical-polymerizable monomer is preferable, and among them, a polyfunctional acrylate or a polyfunctional methacrylate having three or more (meth) acryloyl groups in one molecule is preferable. Specific examples thereof include energy ray-polymerizable monomers described in JP 2010-173091A.

  When the energy ray-polymerizable oligomer and the energy ray-polymerizable monomer are contained in the pressure-sensitive adhesive composition, the total content thereof is 10 parts by weight to 100 parts by weight of the acrylic resin. Within the range of 60 parts by weight, more preferably within the range of 20 parts by weight to 50 parts by weight. Since the crosslink density after irradiation with energy rays is sufficient, proper peelability can be realized, and it is possible to suppress the occurrence of adhesive residue on the laminate side due to the decrease in cohesive force of the pressure-sensitive adhesive composition. Is.

The pressure-sensitive adhesive composition, if necessary, a silane coupling agent, a tackifier, a metal chelating agent, a surfactant, an antioxidant, an ultraviolet absorber, a pigment, a dye, a colorant, an antistatic agent, a preservative, It may contain various additives such as a defoaming agent and a wettability adjusting agent.
Further, in order to improve the removability of the pressure-sensitive adhesive layer of this embodiment, a resin such as a fluorine-based resin may be included.

(Vi) Preferred pressure-sensitive adhesive composition The pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive layer of the present embodiment preferably contains an acrylic resin, an energy ray-polymerizable oligomer, a polymerization initiator, and a cross-linking agent. It is preferable that it is the specific adhesive composition shown in.

  That is, the first pressure-sensitive adhesive composition contains an acrylic resin, an energy ray-polymerizable oligomer, a polymerization initiator, and a crosslinking agent, and the acrylic resin has a mass average molecular weight of 200,000 to 1,000,000. And is obtained by copolymerization of an acrylic acid ester as a main component with a hydroxyl group-containing monomer copolymerizable with the acrylic acid ester, and the polymerization initiator is at a temperature rising rate of 10 ° C./min. It is preferable that the weight loss rate by thermogravimetric measurement when the temperature is raised from 30 ° C. to 190 ° C. and maintained at 190 ° C. for 30 minutes is 50% or less.

  The second pressure-sensitive adhesive composition contains an acrylic resin, an energy ray-polymerizable oligomer, a polymerization initiator, and a crosslinking agent, and the acrylic resin has a mass average molecular weight of 200,000 to 1,000,000. And, which has an acrylic ester as a main component, is obtained by copolymerizing a hydroxyl group-containing monomer and a carboxyl group-containing monomer copolymerizable with the acrylic acid ester, and contains the hydroxyl group-containing monomer and the carboxyl group-containing The mass ratio with the monomer is in the range of 51:49 to 100: 0, and the polymerization initiator is heated from 30 ° C to 190 ° C at a temperature rising rate of 10 ° C / min and maintained at 190 ° C for 30 minutes. It is preferable that the weight reduction rate by thermogravimetry is 50% or less.

  By making the pressure-sensitive adhesive composition the above specific one, the pressure-sensitive adhesive layer of the present embodiment can exhibit high heat resistance capable of sufficiently withstanding the hot pressing conditions in the hot pressing step and excellent low outgassing property. Therefore, not only is it possible to prevent the displacement of the lamination position of each layer and the generation of adhesive residue on the laminate side at the time of peeling, but also to prevent the gas generated from the adhesive layer of this aspect from entering the layers of the laminate during hot pressing. It is also possible to prevent the occurrence of defects and appearance defects.

(Vii) Preparation Method The preparation method of the pressure-sensitive adhesive composition can be the same as the above-mentioned preparation method of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer exhibiting slight adhesion.

(B) Others The pressure-sensitive adhesive layer of the present embodiment may have a thickness capable of obtaining a sufficient pressure-sensitive adhesive force and capable of transmitting energy rays to the inside, and specifically, in the range of 3 μm to 50 μm. Above all, the range of 5 μm to 30 μm is preferable.

2. Substrate As the above-mentioned substrate, those capable of supporting a laminate comprising an adhesive layer and a plurality of functional layers and exhibiting high heat resistance under the heat and pressure conditions in the hot pressing step are preferable.
The term “base material exhibits high heat resistance” means that the coefficient of thermal expansion of the base material in the range of 150 ° C. to 250 ° C. is within the range of 5 ppm / ° C. to 50 ppm / ° C., among which 10 ppm / ° C. to 30 ppm. It is preferably in the range of / ° C.

Examples of such a base material include inorganic base materials such as quartz glass, Pyrex (registered trademark) glass and synthetic quartz plate, resin films, epoxy glass (glass epoxy), resin base materials such as optical resin plate and the like. You can
The base material may or may not have flexibility. When a flexible base material is used, for example, by applying tension in the surface direction of the base material, it is possible to maintain the planarity of the entire adhesive base material. Thereby, when laminating the functional layers, the planarity of each functional layer is also maintained, so that the entire laminate with the adhesive substrate can have planarity.

The resin used for the resin substrate is not particularly limited as long as it exhibits desired heat resistance, and can be appropriately selected according to the type of the adhesive layer formed on the resin substrate.
For example, when the adhesive layer is in the second aspect, the resin that transmits energy rays is preferable as the resin. This is because it is possible to irradiate an energy ray sufficient to reduce the adhesive strength of the adhesive layer through the resin base material.
Among them, polyphenylene sulfide-based resins and polyester-based resins are preferable because they have heat resistance and strength, and are also excellent in dimensional stability, energy ray permeability, rigidity, extensibility, stackability, and chemical resistance.
The resin base material may be a single layer composed of one kind of resin, or may be a multilayer body in which two or more kinds of resin base materials are laminated.

  The base material may be subjected to surface treatment such as corona treatment or primer treatment in order to enhance the adhesion with the adhesive layer.

The thickness of the base material is not particularly limited and can be appropriately selected depending on the material and the presence or absence of flexibility.
The form of the base material is not particularly limited, and examples thereof include a plate shape, a sheet shape, a film shape, and a tape shape depending on the presence or absence of flexibility. Further, the base material may be in a roll shape or a sheet shape.

The base material may or may not have transparency, but when the adhesive layer is the second aspect, the base material preferably has transparency. This is because it is possible to irradiate with sufficient energy rays from the base material side to reduce the adhesive force.
Above all, it is preferable that the above-mentioned base material in the case where the adhesive layer is in the second mode transmits energy rays having a wavelength of 400 nm or less. This is because it is possible to irradiate through the base material an energy ray sufficient to cause the adhesive layer to exhibit releasability.
The transmittance of energy rays when the substrate has transparency can be appropriately set according to the type of energy rays and the like.

3. Method for Forming Adhesive Substrate The adhesive substrate in this step can be usually formed by applying the adhesive composition on one surface of the substrate, depending on the type of the adhesive layer. The method for applying the pressure-sensitive adhesive composition is not particularly limited, and a conventionally known method can be used. For example, the coating method disclosed in JP-A-2014-234460 can be applied.

In the case of forming the pressure-sensitive adhesive layer of the first aspect on the substrate, a method of applying the pressure-sensitive adhesive composition according to the type of the pressure-sensitive adhesive composition and then curing it by heating or light irradiation is used.
When using the pressure-sensitive adhesive composition of the first aspect, the above-mentioned pressure-sensitive adhesive composition is applied and the epoxy thermosetting resin in the coating layer is cured by heating. The heating temperature is, for example, about 50 ° C to 150 ° C, preferably about 90 ° C to 120 ° C. Further, the heating time can be appropriately adjusted depending on the heating temperature. For example, if the heating temperature is in the range of 90 ° C to 150 ° C, the heating time can be in the range of 1 minute to 240 minutes, preferably in the range of several minutes to 60 minutes. If the heating temperature is in the range of 50 ° C to 90 ° C, the heating time can be set in the range of 24 hours to 168 hours, preferably in the range of 48 hours to 120 hours.
Further, when the pressure-sensitive adhesive composition of the second aspect is used for the formation, after the pressure-sensitive adhesive composition is applied, the coating layer is irradiated with light to cure the photocurable resin. The conditions of light irradiation are appropriately set according to the type of photocurable resin. Since the pressure-sensitive adhesive composition of the second aspect contains a crosslinking agent, when the coating layer is dried, crosslinking is formed between the acrylic resins in the layer. The coating layer may be heated. This is because it is possible to accelerate the crosslinking reaction of the acrylic resin. The heating temperature can be set appropriately.

  On the other hand, when the pressure-sensitive adhesive layer of the second aspect is formed on the substrate, the pressure-sensitive adhesive composition is applied and then dried. When the coating layer is dried, crosslinks are formed between the acrylic resins in the layer. The drying conditions and the like are not particularly limited.

B. Laminating Step The laminating step in the present invention is a step of laminating a plurality of functional layers on the adhesive layer of the adhesive substrate to form a laminate with an adhesive substrate.

  In this step, among the plurality of functional layers laminated on the adhesive substrate, the functional layer directly arranged on the adhesive layer is fixed by the adhesive force of the adhesive layer, and therefore has flatness. You can Further, it is possible to prevent the occurrence of positional deviation when laminating other functional layers. Thereby, the flatness of the laminated body before the hot pressing step can be maintained. Further, it is possible to prevent the displacement of the position where the laminate is arranged with respect to the adhesive substrate during hot pressing.

  The functional layer to be laminated in this step can be appropriately selected depending on the application of the laminate. For example, when the laminate obtained by the present invention is used as a multilayer printed wiring board, the functional layer is, for example, an insulating layer or a wiring pattern layer. The materials and forming methods of the various functional layers are not particularly limited, and conventionally known materials and forming methods can be applied.

In the laminated body with the adhesive base material, the adhesive base material may be disposed on at least one surface in the laminating direction of the laminated body before the hot pressing step, but as shown in FIG. The adhesive base materials 20 may be arranged on both surfaces of the previous laminated body 10 'in the laminating direction.
By disposing the adhesive base materials on both surfaces of the laminated body in the laminating direction, the laminated body can be more firmly fixed. Further, when the laminated body is usually hot pressed, it is carried out through a protective film for hot pressing. In this step, the laminated body before the hot pressing step is sandwiched by a pair of adhesive base materials facing each other in the laminating direction. By doing so, one of the adhesive base materials can function as a protective film for hot pressing.

C. Hot-pressing step The hot-pressing step in the present invention is a step of heating and pressurizing the above-mentioned adhesive substrate-attached laminate.

  The heating temperature and the pressing force such as the pressing force in this step may be any conditions as long as it is possible to improve the interlayer adhesion of each functional layer constituting the laminate before hot pressing, and the material of each functional layer It can be appropriately set according to the above.

D. Peeling Step The peeling step in the present invention is a step of peeling the adhesive substrate from the laminate with the adhesive substrate.

The peeling method may be any method as long as it can be peeled between the pressure-sensitive adhesive layer of the pressure-sensitive adhesive substrate and the laminate, and can be appropriately selected according to the composition of the pressure-sensitive adhesive layer. In the case of the pressure-sensitive adhesive layer of the first aspect, a method of applying a force between the layers of the laminate and the pressure-sensitive adhesive layer by utilizing its slight pressure-sensitive adhesiveness can be mentioned. Specifically, a method of peeling the adhesive layer by hand or a machine, a method of adsorbing and peeling an adhesive base material with air, etc., and a transfer target having a strong adhesive layer having a stronger adhesive force than the adhesive layer are bonded. However, a method of peeling the adhesive base material can be used by utilizing the difference in adhesive force between the adhesive layer and the strong adhesive layer.
On the other hand, with the pressure-sensitive adhesive layer of the second aspect, the laminate can be easily peeled off by irradiating with energy rays. The irradiation condition of the energy ray is not particularly limited as long as it can irradiate the energy ray sufficient to reduce the adhesive force, and for example, the irradiation condition described in JP 2012-031316 A is applied. You can

E. Arbitrary Steps The method for manufacturing a laminate of the present invention may have optional steps in addition to the above-mentioned steps, depending on the application of the laminate. Hereinafter, the optional steps assumed in the present invention will be described.

1. Cutting Process In the present invention, a cutting process for cutting the laminate with the adhesive substrate may be provided between the hot pressing process and the peeling process.

Conventionally, when cutting a laminated body that has been subjected to a hot pressing step, it is necessary to separately cut the laminated body using a dicing tape while being fixed on the support layer. Here, in the laminating step, it is also conceivable to fix the laminated body before the hot pressing step on the base material by using a dicing tape, but the dicing tape can usually endure the hot pressing condition in the hot pressing step. Since the laminate does not have heat resistance, the laminate is not sufficiently fixed on the adhesive layer, misalignment occurs during the hot pressing process, the adhesive layer is reduced in aggregation, and adhesive residue occurs during peeling. There is a problem that a series of processes from the process to the cutting process cannot be continuously performed.
On the other hand, according to the present invention, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive substrate exhibits heat resistance capable of withstanding hot pressing conditions in the hot pressing step, and also has sufficient tackiness for fixing the laminate, It can function as a dicing tape in the cutting process. Further, the pressure-sensitive adhesive layer in the present invention has a feature that adhesive residue hardly occurs on the laminate side when peeled. As a result, a series of steps from the laminating step to the peeling step including the cutting step can be continuously performed while being fixed on a single adhesive base material, and the steps can be simplified. it can.

  FIG. 3 is a process drawing showing a part of another example of the method for manufacturing a laminate of the present invention, where FIG. 3 (a) is a hot pressing process, FIG. 3 (c) is a cutting process, and FIG. 3 (d). Is a peeling process. Note that, in FIG. 3, the preparation process and the laminating process can be the same as those in FIGS.

When the laminate is cut, only the laminate may be cut, or the entire laminate with the adhesive substrate may be cut.
The method for cutting the laminate is not particularly limited, and can be appropriately selected depending on the material of the laminate and the like.

2. Chemical Solution Processing Step In the present invention, a chemical solution processing step may be provided between the hot pressing step and the peeling step.

For example, in the case of manufacturing a laminated body for a multilayer wiring board using the present invention, through holes such as through holes and vias are formed in the laminated body that has undergone the hot pressing process, and the metal remaining in the through holes is Desmearing is performed to remove residues (smear) such as resin. In addition, a plating process is performed to form a plating layer on the inner wall of the through hole.
However, when these treatments are carried out in a wet process, the chemical solution used may erode the outermost layer of the laminate, resulting in a problem such that the eroded functional layer becomes a foreign substance and contaminates the laminate. There is.
According to the present invention, the laminated body after the hot pressing step is subjected to the chemical treatment while being fixed to the adhesive substrate, so that the adhesive substrate functions as a protective layer to form a laminated body by the chemical liquid. It is possible to prevent erosion and pollution of the. Further, after the chemical solution treatment, the occurrence of adhesive residue on the laminate side is suppressed, and the adhesive base material can be easily peeled off. Therefore, a series of steps from the lamination step to the peeling step including the chemical solution treatment step. This can be performed in a state of being fixed on a single adhesive base material, and the process can be simplified.

  The chemical liquid treatment in the present invention means, for example, a treatment performed in a wet process. Specifically, an etching process for forming a through hole in the laminate by wet etching, a desmear process for removing smear in the through hole formed in the laminate, a plating process for forming a plating layer on the inner wall of the through hole, etc. Is mentioned.

The chemical treatment method may be any method as long as the adhesive substrate can function as a protective layer and can prevent the outermost layer of the laminate from being eroded by the chemical, and a conventionally known method depending on the treatment content. Can be applied. The type of chemical solution used can be appropriately selected depending on the processing content.
Further, in carrying out this step, it is preferable that the adhesive substrate is arranged on the surface (outermost layer) in the laminating direction of the laminate, which is desired to be protected from chemical treatment (non-chemical treatment surface). . Out of the outermost layer of the laminate, when one is a chemical liquid treatment surface and the other is a chemical liquid non-treatment surface, the adhesive base material is arranged on the chemical liquid non-treatment surface, thereby the chemical liquid non-treatment surface. This is because it is possible to prevent the contamination of the above and to sufficiently protect it.
In addition, an adhesive base material may be arranged on both surfaces of the laminate in the laminating direction. This is because by sandwiching the laminate with a pair of adhesive base materials that face each other in the laminating direction, both surfaces of the laminate can be efficiently protected when it is desired to protect the surfaces from contamination and the like due to chemical treatment.

3. Positioning Step In the present invention, it is preferable that the laminating step includes a positioning step of determining the position of the laminated body in plan view with respect to the adhesive substrate.
When the positioning accuracy of the laminated body with respect to the adhesive substrate in plan view is low, due to the positioning error of each functional layer that constitutes the laminated body, the printing and the placement of parts etc. are accurately performed at a desired position on the laminated body. Problems that cannot be performed, such as electrical continuity between the terminals of the laminated body when the laminated body is used for electronic component applications such as a multilayer wiring board, occur.
On the other hand, in the present invention, since the lowermost functional layer is fixed on the adhesive substrate in the laminating step, other functional layers are laminated while determining the position in plan view with respect to the lowermost functional layer. It is possible.
In this way, by determining the position of the laminated body with respect to the adhesive substrate in plan view, the positioning accuracy of the laminated body with respect to the adhesive substrate is improved, so conduction in the laminated body is prevented, and printing or printing is performed at a desired position. It is possible to accurately arrange the parts and the like.

  The positioning method is not particularly limited as long as it is a method capable of highly accurately determining the position of each functional layer and the laminate in plan view with respect to the adhesive substrate. For example, a method may be used in which an alignment mark is formed on an adhesive substrate, and the functional layers are arranged and laminated on the basis of the alignment mark. Further, the alignment mark can be used as a reference when printing on a laminate or arranging components and the like.

F. Applications The method for producing a laminate of the present invention can be widely used for producing a laminate through a hot pressing step. Among them, by using an adhesive base material having an adhesive layer exhibiting removability and heat resistance, it is possible to simplify the production process, and since it is possible to prevent contamination of the laminate in the production process, It is preferably used for manufacturing a laminate used for electronic parts.
Further, the laminated body obtained by the present invention can be suitably used as, for example, a multilayer chip antenna, a multilayer capacitor, a multilayer printed wiring board, a flexible printed wiring board, a module substrate such as an IC package substrate, and the like.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, has substantially the same configuration as the technical idea described in the scope of the claims of the present invention, and has any similar effect to the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1]
(Preparation of adhesive composition)
An acrylic copolymer (mass average molecular weight) containing methyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and 2-hydroxyethyl acrylate as monomer units at a ratio of 50: 40: 0.5: 9.5 on a mass basis, respectively. : 200,000, glass transition temperature: 6 ° C.) were used.
To this ethyl acetate solution of acrylic copolymer (adhesive, solid content 35% by mass), 3 parts by weight of isocyanate cross-linking agent (L45, manufactured by Soken Chemical Co., Ltd.) (solid content ratio to adhesive) was added, and further energy was added. A linear polymerizable oligomer (NK oligo U-10PA (urethane acrylate oligomer), manufactured by Shin Nakamura Chemical Co., Ltd.) 10 parts by weight and a photoinitiator (3% with respect to an ultraviolet curable resin) are added as MEK as a diluent solvent to obtain an adhesive. A composition was obtained.

(Preparation of adhesive substrate)
A 25 μm-thick polyimide film (IF70, manufactured by SKC Kolon Co., Ltd.) as a base material was coated with the pressure-sensitive adhesive composition so that the thickness would be 10 μm after drying, and dried at 110 ° C. for 2 minutes to give a slight adhesive property. Was formed on the adhesive layer. A 38 μm-thick PET separator film (SP-PET-O1, manufactured by Mitsui East Cello Co., Ltd.) was laminated on the pressure-sensitive adhesive layer, and irradiated with ultraviolet rays having a wavelength of 365 nm so that the integrated irradiation amount was 300 mJ / cm ² . Then, it was cured at 40 ° C. for 3 days, and the PET separator film was peeled off to obtain an adhesive base material. The adhesive substrate had an outgas generation amount of 2.5 μg / cm ² and an initial adhesive force of the adhesive layer of 1 N / 25 mm.

(Lamination process to peeling process)
A copper foil was laminated on the adhesive layer of the adhesive base material and subjected to a heat press treatment at 200 ° C. and 3 MPa for 1 hour, and then the adhesive base material was peeled off from the copper foil.

[Example 2]
Each step was performed in the same manner as in Example 1 except that 10 parts by mass of an ultraviolet curable resin (502H, manufactured by Arakawa Chemical Co., Ltd.) was further added to the pressure-sensitive adhesive composition of Example 1.

[Example 3]
Each step was performed in the same manner as in Example 1 except that an epoxy resin plate was used instead of the copper foil, and the condition of the hot press treatment was 180 ° C. and 2 MPa for 2 hours.

[Example 4]
Each step was performed in the same manner as in Example 2 except that an epoxy resin plate was used instead of the copper foil, and the hot press treatment conditions were 180 ° C. and 2 MPa for 2 hours.

[Example 5]
(Preparation of adhesive composition)
Acrylic copolymer resin (mass average) containing methyl acrylate, 2-ethylhexyl acrylate, acrylic acid, and 2-hydroxyethyl acrylate as monomer units at a ratio of 50: 40: 0.5: 9.5 on a mass basis, respectively. (Molecular weight: 200,000, glass transition temperature: 6 ° C.) was used. 100 parts by weight of an ethyl acetate solution (solid content: 35% by mass) of the acrylic copolymer resin, solid epoxy resin (bisphenol A type epoxy resin, epoxy equivalent: 480 g / eq., Mass average molecular weight: 900, trade name : JER1001, Mitsubishi Chemical Co., Ltd.) 14 parts by weight, and 2-methyl-4-ethylimidazole (trade name: Caazole 2E4MZ, Shikoku Kasei Co., Ltd.) 0.35 parts by weight as a curing agent, toluene and methyl ethyl ketone. In a mixed solvent (trade name: KT-11, mass ratio 1: 1, manufactured by DIC Graphics Co., Ltd.) and stirred with a disper at a rotation speed of 500 rpm for 30 minutes, and then allowed to stand at room temperature until air bubbles disappear, thereby sticking An agent composition was obtained.

(Preparation of adhesive base material)
The pressure-sensitive adhesive composition obtained above was subjected to an easy release treatment of a polyester film (trade name: SP-PET-01, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) having a thickness of 38 μm, which was subjected to an easy release treatment with a silicone release agent on one surface. After coating the entire surface with an applicator on the surface, it was dried in a drying oven at 110 ° C. for 1 minute to form an adhesive layer having a slight adhesiveness of 10 μm. A 25 μm thick polyimide film substrate (trade name: Kapton 100H, manufactured by DuPont Toray) is laminated on the adhesive layer, and after curing at 60 ° C. for 120 hours, the polyester film is peeled off to give an adhesive substrate. Got The adhesive substrate had an outgas generation amount of 2.2 μg / cm ² and an initial adhesive force of the adhesive layer of 0.30 N / 25 mm.

(Lamination process to peeling process)
A copper foil was laminated on the adhesive layer of the adhesive base material and subjected to a heat press treatment at 200 ° C. and 3 MPa for 1 hour, and then the adhesive base material was peeled off from the copper foil.

[Example 6]
(Preparation of adhesive composition)
Acrylic adhesive (trade name: N-4498, acrylic polymer + energy ray polymerizable oligomer, mass average molecular weight of acrylic polymer: about 400,000, energy ray polymerizable oligomer: polyurethane acrylate oligomer, hydroxyl group content in acrylic polymer Mass ratio of monomer to carboxyl group-containing monomer: 30/1, solid content: 40%, based on 100 parts by weight of a polymerization initiator (trade name: IRGACURE754, photoradical generator, solid content) : 100%, manufactured by BASF Japan Ltd., 1.4 parts by weight, and 1.5 parts by weight of a crosslinking agent (trade name: Coronate L, isocyanate-based crosslinking agent, solid content: 75%, manufactured by Nippon Polyurethane Co., Ltd.) , A mixed solvent of toluene and methyl ethyl ketone (trade name: KT11, mass ratio 1: 1, Diluted with IC graphics Co., Ltd.) 180 parts by weight, followed by stirring for 30 minutes at a rotation speed 500rpm with a disper to obtain a pressure-sensitive adhesive composition by allowing to stand at room temperature until no more air bubbles.

(Preparation of adhesive base material)
The obtained pressure-sensitive adhesive composition was subjected to an easy release treatment with a silicone-based release agent on one surface, and had a thickness of 38 μm and was subjected to an easy release treatment on a polyester film (trade name: SP-PET-01, manufactured by Mitsui Chemicals Tohcello). After the entire surface was coated with an applicator, it was dried in a drying oven at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 10 μm. The pressure-sensitive adhesive layer was a pressure-sensitive adhesive layer that was peeled off by irradiation with energy rays. On the surface of the formed adhesive layer, a biaxially stretched polyester film substrate having a thickness of 50 μm (trade name: Lumirror S56, heat shrinkage (JIS C2151 compliant, 150 ° C. × 30 min): MD 0.5%, TD 0 .3%, film thickness: 50 μm, manufactured by Toray Industries, Inc.) and cured at 40 ° C. for 72 hours, and the polyester film that has been subjected to the easy peeling treatment is peeled off to give an outgas generation amount of 10 μg / cm ² , the initial stage. An adhesive base material having an adhesive force of 0.40 N / 25 mm and a weight loss rate of the polymerization initiator in the adhesive layer of 12% was obtained.

(Lamination process to peeling process)
A copper foil is laminated on the adhesive layer of the adhesive substrate, and a heat press treatment is performed at 200 ° C. and 3 MPa for 1 hour, and then a H. bulb lamp manufactured by Fusion Co., Ltd. is used as a light source from the adhesive substrate side. The adhesive substrate was peeled from the copper foil by irradiating with ultraviolet rays (integrated light amount 500 mJ / cm ² ).

[Comparative example]
Each step was performed in the same manner as in Example 1 except that the ultraviolet curable resin and the initiator were removed from the pressure-sensitive adhesive composition of Example 1.

[Evaluation]
Regarding Examples 1 to 6 and Comparative Example, the presence or absence of adhesive residue (width of 1 mm or more) on the surface of the copper foil or the epoxy resin plate after peeling the adhesive substrate, which was in contact with the adhesive layer, was examined by an optical microscope. (VHX-600, manufactured by Keyence Corporation, magnification 200).
In the comparative example, adhesive residue was found on the surface of the copper foil, but in Examples 1 to 6, it was confirmed that there was no adhesive residue on the peeled surface as compared with the comparative example. From the above, it was suggested that the present invention can suppress contamination due to adhesive residue on the peeled surface.

1a, 1b, 1c ... Functional layer 10 ... Laminated body (after hot pressing)
10 '... Laminated body (before heat pressing)
11 ... Heat-resistant base material 12 ... Adhesive layer 20 ... Adhesive base material 30 ... Laminated body with adhesive base material

Claims (3)

A preparatory step of preparing an adhesive substrate having a substrate and an adhesive layer formed on one surface of the substrate,
Laminating step of laminating a plurality of functional layers on the adhesive layer of the adhesive substrate, to form a laminate with an adhesive substrate,
A hot pressing step of heating and pressurizing the laminate with the adhesive substrate,
A peeling step of peeling the adhesive base material from the laminate with the adhesive base material,
Have
The adhesive layer showed slightly adhesive, Ri fixable Sodea the position of the functional layer,
The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition containing an acrylic resin, a crosslinking agent, a photocurable resin, and a photoinitiator, and the crosslinked body of the acrylic resin and the photocurable resin are cured. A method for producing a laminated body, comprising: Between the stripping step and the heat pressing step, method for producing a laminate according to claim 1, characterized in that it comprises a cutting step of cutting the adhesive base material-attached laminate. The method for manufacturing a laminate according to claim 1 or 2 , further comprising a chemical treatment step between the hot pressing step and the peeling step.