Release layer, molded article having a release layer, and release agent

Abstract

To provide a molded article with a release layer that offers superior wettability with a released body and exhibits light peelability.SOLUTION: A molded article includes a substrate and a release layer. The release layer has a surface free energy of 30 mJ / m2 or more and 60 mJ / m2 or less. The release layer includes a crosslinked polymer comprising an X component and a Y component (excluding polyester resin), where the polymer comprises the Y component in the range of 1 mol or more and 30 mol or less relative to the X component 100 mol, and where the polymer has a hydroxyl value of 10 mgKOH / g or more and 50 mgKOH / g or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a release layer, a molded article comprising a release layer, and a release agent. [Background technology]

[0002] Conventionally, in the manufacturing process of circuit boards, release agents and release films (films coated with release agents) have been used to facilitate the separation of the mold from the molded object and to ensure product uniformity, stability, and ease of handling. Common release agents include silicone-based release agents, fluorine-based release agents, and long-chain alkyl-based release agents.

[0003] However, while silicone-based release agents have excellent release properties, their use in electronic components is difficult because the silicone component easily transfers to the object being released. Fluorine-based release agents have excellent release properties and heat resistance, but they are expensive and have poor wettability. Long-chain alkyl-based release agents have better wettability than silicone-based and fluorine-based release agents, but their release force tends to increase after heating. Furthermore, long-chain alkyl-based release agents do not always have sufficient release properties. In addition, heat and pressure may be applied to the release film during the manufacturing process of circuit boards. Long-chain alkyl-based release agents have the problem of not being able to fully demonstrate their performance as release agents, due to their tendency to increase in release force after heating.

[0004] Patent Document 1 (Japanese Unexamined Patent Publication No. 2010-144046) discloses a mold release agent that can prevent repulsion when applying adhesive resin to a mold release agent and maintain good peeling performance from adhesive resin film, and which contains poly(meth)acrylate as the main component, which contains (A) alkyl group or aryl group-terminated mono or polyalkylene glycol (meth)acrylate units and (B) alkyl (meth)acrylate units of alkyl groups having 1 to 30 carbon atoms.

[0005] Patent Document 2 (Japanese Patent Publication No. 2007-002092) discloses a mold release agent that has lighter release properties than silicone resin mold release agents and does not migrate, and contains an active ingredient which is a prepolymer copolymer of at least alkyl (meth)acrylate and hydroxyalkyl (meth)acrylate crosslinked with an isocyanate group-containing compound.

[0006] Patent Document 3 (Japanese Patent Publication No. 2014-151481) discloses a laminated polyester film characterized by having a coating layer formed on at least one side of the polyester film from a coating solution containing a release agent and an activated methylene block isocyanate compound, which is a release polyester film that exhibits less deterioration of release properties due to heat during processing. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2010-144046 [Patent Document 2] Japanese Patent Publication No. 2007-002092 [Patent Document 3] Japanese Patent Publication No. 2014-151481 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, the technology described in Patent Document 1 has a peeling force greater than 583 mN / 20 mm, and there is a need for a release agent with a lighter peeling force.

[0009] Furthermore, the technology described in Patent Document 2 has the problem of insufficient wettability of the mold release agent.

[0010] Furthermore, in the technology described in Patent Document 3, the peeling force after heating is 1080 mN / cm or more, indicating heavy peeling after heating. Moreover, the peeling force after heating is 710 mN / cm or more greater than the peeling force under normal conditions, which is a problem as it does not adequately suppress the increase in peeling force due to heating.

[0011] Therefore, the first invention of the present invention aims to provide a release layer that has good wettability with the object to be released and has light release properties, a molded article equipped with the release layer, and a release agent.

[0012] Furthermore, the second invention of the present invention aims to provide a release layer having slight release properties both before and after heating, a molded article equipped with the release layer, and a release agent. [Means for solving the problem]

[0013] (1) The release layer according to the first invention of the present invention has a surface free energy of 30 mJ / m 2 More than 60mJ / m 2 The following conditions apply, and the normal peeling force is between 50 mN / 50 mm and 400 mN / 50 mm.

[0014] (2) Preferably, in the release layer according to the first invention, the release layer is formed by crosslinking a polymer containing component X represented by the following formula (1) and component Y represented by the following formula (2).

[0015] [ka]

[0016] In equation (1), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3.

[0017] [ka]

[0018] In equation (2), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0019] (3) In the release layer according to the first invention, preferably, the polymer contains the Y component in a range of 1 mol or more and 30 mol or less with respect to 100 mol of the X component.

[0020] (4) In the release layer according to the first invention, preferably, the polymer is a polymer further containing a Z component represented by the following formula (3).

[0021]

Chemical formula

[0022] In formula (3), R3 is (C a H 2a O) q (a is an integer of 1 or more and 4 or less, q is an integer of 2 or more and 30 or less), R4 is H or CH3, and R5 is (C b H 2b+1 )(b is an integer of 1 or more and 20 or less).

[0023] (5) The second invention of the present invention is a release layer having a normal peeling force of 50 mN / 50 mm or more and 400 mN / 50 mm or less, and a peeling force after heating of 2 times or less of the normal peeling force.

[0024] (6) In the release layer of the second invention, preferably, the surface free energy is 30 mJ / m 2 or more and 60 mJ / m 2 or less.

[0025] (7) In the release layer of the second invention, preferably, the release layer is formed by crosslinking a polymer containing an X component represented by the following formula (4), a Y component represented by the following formula (5), and a Z component represented by the following formula (6).

[0026]

Chemical formula

[0027] In formula (4), R1 is (C n H 2n+1)(n=an integer between 8 and 20), R4 represents H or CH3.

[0028] [ka]

[0029] In equation (5), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0030] [ka]

[0031] In equation (6), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 5 and 30), R4 is H or CH3, R5 is (C b H 2b+1 This shows that (b = an integer between 1 and 20).

[0032] (8) Preferably, in the release layer according to the present invention, the polymer has a weight-average molecular weight of 5,000 or more and 150,000 or less.

[0033] (9) Preferably, in the release layer according to the present invention, the hydroxyl value of the polymer is 1 mg KOH / g or more and 50 mg KOH / g or less.

[0034] (10) Preferably, in the release layer according to the present invention, the polymer is crosslinked with a crosslinking agent.

[0035] (11) Preferably, in the release layer according to the present invention, R1 in formula (1) is linear.

[0036] (12) Preferably, in the release layer according to the present invention, the polymer contains 5 moles or more and 30 moles or less of component Y and 1 mole or more and 30 moles or less of component Z per 100 moles of component X.

[0037] (13) The molded article according to the present invention comprises a base material and the above-mentioned release layer disposed on the surface of the base material.

[0038] (14) The release agent according to the first invention of the present invention comprises a polymer containing component X represented by the following formula (1) and component Y represented by the following formula (2), and a crosslinking agent.

[0039] [ka]

[0040] In equation (1), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3.

[0041] [ka]

[0042] In equation (2), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0043] (15) The mold release agent according to the second invention of the present invention is a mold release agent comprising a polymer containing component X represented by the following formula (4), component Y represented by the following formula (5), and component Z represented by the following formula (6), and a crosslinking agent.

[0044] [ka]

[0045] In equation (4), R1 is (C n H 2n+1 (n = an integer between 8 and 20), R4 represents H or (CH3).

[0046] [ka]

[0047] In equation (5), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or (CH3).

[0048] [ka]

[0049] In equation (6), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 5 and 30), R4 is H or CH3, R5 is (C b H 2b+1 This shows that (b = an integer between 1 and 20). [Effects of the Invention]

[0050] According to the first invention of the present invention, it is possible to provide a release layer having good wettability with the object to be released and light release properties, a molded article equipped with the release layer, and a release agent.

[0051] Furthermore, according to the second invention of the present invention, it is possible to provide a release layer having slight release properties both before and after heating, a molded article equipped with the release layer, and a release agent. [Modes for carrying out the invention]

[0052] <Embodiment 1> A release layer according to one embodiment of the first invention of the present invention has a surface free energy of 30 mJ / m 2 More than 60mJ / m 2 The following conditions apply, and the normal peeling force is between 50 mN / 50 mm and 400 mN / 50 mm.

[0053] The aforementioned release layer has a surface free energy of 30 mJ / m 2 More than 60mJ / m 2Therefore, the wettability with the mold release material is good. In this specification, surface free energy is the contact angle θ between water and methylene iodide (CH2I2) in contact with the surface of the mold release layer, measured using a contact angle meter (FACE Contact Angle Meter CA-X manufactured by Kyowa Interface Science Co., Ltd.) under conditions of 20°C and 65%RH. w and θ y Measure and from these measurements, γ according to the method described in Journal of Applied Polymer Science, vol.13, pp.1741-1747 (1969) sh (Hydrogen bonding force component term) and γ sd The (hydrogen dispersion force component term) is calculated, and the sum of each component is the surface free energy γ s This is the value calculated as follows: Specifically, the hydrogen bonding force component term γ in surface energy. sh And, the hydrogen dispersion force component term γ in the surface energy of polyester film sd The contact angle of water with respect to the surface of the release layer is θ. w , and the contact angle θ of methylene iodide (CH2I2) y from, 1 + cosθ w =[2×(γ sd ) 1 / 2 ×{(γ wd ) 1 / 2 / γ w}]+[2×(γ sh ) 1 / 2 ×{(γ wh ) 1 / 2 / γ w}]...Formula (A) 1 + cosθ y =[2×(γ sd ) 1 / 2 ×{(γ yd ) 1 / 2 / γ y}]+[2×(γ sh ) 1 / 2 ×{(γ yh ) 1 / 2 / γ y}]...Formula (B) It can be found by solving the following two simultaneous equations. Note that γ in the above equation w gamma y These are the surface tensions of water and methylene iodide (CH2I2), respectively, and γwd and γ yd are the dispersion force component terms in the respective surface tensions, and γ wh and γ yh are the hydrogen bond force component terms in the respective surface tensions. Note that γ w = γ wd + γ wh and γ y = γ yd + γ yh . Specifically, from the surface tension of water, γ w = 72.8 mJ / m 2 and γ wd = 21.8 mJ / m 2 and γ wh = 51.0 mJ / m 2 and from the surface tension of methylene iodide, γ y = 50.8 mJ / m 2 and γ yd = 48.5 mJ / m 2 and γ yh = 2.3 mJ / m 2 are substituted to obtain γ sd and γ sh .

[0054] The surface free energy is preferably 40 mJ / m 2 or more and 60 mJ / m 2 or less, and more preferably 50 mJ / m 2 or more and 60 mJ / m 2 or less.

[0055] The release layer has a normal peel force of 50 mN / 50 mm to 400 mN / 50 mm, and therefore has light peelability. The normal peel force is preferably 50 mN / 50 mm to 300 mN / 50 mm, and more preferably 50 mN / 50 mm to 250 mN / 50 mm. In this specification, the normal peel force is the value of the T-shaped peel strength measured in the following steps. Adhesive tape ("31B" manufactured by Nitto Denko Corporation) is attached to the surface of the release film, and after being pressed with a pressure roller with a linear pressure of 5 kgf / mm, it is left for 20 hours under conditions of a temperature of 22°C and a humidity of 60%. The release film with the adhesive tape attached is shredded into strips with a width of 25 mm and a length of 150 mm. One end of the adhesive tape is fixed, and one end of the release film is supported, and the release film side is pulled at a speed of 300 mm / min to peel it off, and the T-shaped peel strength is measured. A tensile testing machine ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) was used to measure the T-shaped peel strength.

[0056] In a release layer according to one embodiment of the present invention, the release layer is preferably formed by crosslinking a polymer containing component X represented by the following formula (1) and component Y represented by the following formula (2).

[0057] [ka]

[0058] In equation (1), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3.

[0059] [ka]

[0060] In equation (2), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0061] In formula (1) representing component X, R1 is an alkyl group with 8 to 20 carbon atoms (n). If the number of carbon atoms (n) is 7 or less, component X loses its release properties and becomes sticky. On the other hand, if the number of carbon atoms (n) is 21 or more, the flexibility of component X is impaired, and the wettability of the release layer coating surface becomes insufficient. The number of carbon atoms (n) is preferably 10 to 18, and more preferably 12 to 16. Furthermore, R1 may be linear or branched. Note that a linear R1 is preferred because it tends to make the release layer easier to peel off.

[0062] In formula (1) representing component X, R4 is either H or CH3, and both are preferred. As the raw material for component X, the monomer shown in formula (7) below can be used.

[0063] [ka]

[0064] In equation (7), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3. Specifically, lauryl (meth)acrylate and stearyl (meth)acrylate can be used as raw materials for component X.

[0065] In R2 of formula (2) representing the Y component, the number of carbon atoms m is between 1 and 10. If the number of carbon atoms m is 11 or more, the crosslinking density becomes sparse, the cohesive force of the release layer itself weakens, and the peeling force becomes heavier. The number of carbon atoms m is preferably between 2 and 8, and more preferably between 2 and 4.

[0066] In formula (2) representing the Y component, R4 is either H or CH3, and both are preferred. As the raw material for component Y, the monomer shown in the following formula (8) can be used.

[0067] [ka]

[0068] In equation (8), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3. Specifically, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc., can be used as raw materials for component Y.

[0069] The polymer preferably has a weight-average molecular weight of 5,000 or more and 150,000 or less. In this specification, the weight-average molecular weight is the value calculated using GPC (Gravity Propagation) to represent the weight-average molecular weight on a polystyrene basis. If the weight-average molecular weight of the polymer is less than 5,000, the entanglement between polymer chains is weak, resulting in a weak film strength when the release layer is molded, which may cause problems in post-processing steps such as the release layer detaching due to friction. On the other hand, if the weight-average molecular weight of the polymer exceeds 150,000, the viscosity of the polymer increases, making it difficult to mold the release layer. The weight-average molecular weight of the polymer is more preferably 20,000 or more and 120,000 or less.

[0070] The hydroxyl value of the polymer is preferably 1 mg KOH / g or more and 50 mg KOH / g or less. If the hydroxyl value of the polymer is less than 1 mg KOH / g, there are few functional groups that can be crosslinked by the crosslinking agent, and the release layer does not harden. If the hydroxyl value of the polymer exceeds 50 mg KOH / g, the release properties of the release layer are impaired due to hydrogen bonding of hydroxyl groups. The hydroxyl value of the polymer is more preferably 10 mg KOH / g or more and 50 mg KOH / g or less.

[0071] The polymer is preferably crosslinked with a crosslinking agent. Suitable crosslinking agents include polyisocyanates, melamines, epoxy, aluminum chelates, titanium chelates, UV-curable resins, or mixtures of two or more of these. Among these, polyisocyanates are preferred because they can be reacted under mild conditions. Crosslinking with aluminum chelates or titanium chelates may be undesirable depending on the application due to the presence of metal components. The amount of crosslinking agent added relative to the total amount of polymer raw materials is preferably 0.5% to 10% by mass, and more preferably 1% to 3% by mass.

[0072] The polymer preferably contains 1 mole to 30 moles of component Y per 100 moles of component X. This results in a polymer with good wettability and easy peeling. It is even more preferable that the blending ratio of component X to component Y in the polymer is 10 moles to 25 moles of component Y per 100 moles of component X.

[0073] <Embodiment 2> The release layer according to one embodiment of the first invention of the present invention consists of a polymer that includes the X and Y components described in Embodiment 1, in addition to the Z component represented by the following formula (3).

[0074] [ka]

[0075] In equation (3), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 2 and 30), R4 is H or CH3, R5 is (C b H 2b+1 This shows that (b = an integer between 1 and 20). The inclusion of component Z in the polymer further improves the wettability of the release layer.

[0076] In R3 of formula (3) representing the Z component, q is preferably between 2 and 30. If q is 1 or less, the surface free energy becomes low, and the wettability of the release layer deteriorates. On the other hand, if q is 31 or more, the long-chain alkyl group of the X component that exhibits release properties becomes less likely to be exposed at the air interface, and there is a risk of severe delamination of the release layer. A value of q between 2 and 25 is even more preferable.

[0077] In formula (3) showing the Z component, R3 is preferably an integer between 1 and 4. If a is 5 or greater, the hydrophobicity increases, which may worsen the wettability. A value of a between 2 and 4 is even more preferable.

[0078] In R5 of equation (3) representing the Z component, b is preferably an integer between 1 and 20. If b is 21 or greater, the hydrophilic portion of the Z component may not be easily exposed on the surface, resulting in insufficient wettability. A value of b between 1 and 10 is even more preferable.

[0079] The polymer preferably contains 1 mole to 30 moles of component Y and 1 mole to 30 moles of component Z per 100 moles of component X. This results in a polymer with good wettability and easy peeling. It is even more preferable that the amounts of components X, Y, and Z in the polymer be 10 moles to 25 moles of component Y and 5 moles to 25 moles of component Z per 100 moles of component X.

[0080] As the raw material for component Z, the monomer shown in formula (9) below can be used.

[0081] [ka]

[0082] In equation (9), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 2 and 30), R4 is H or CH3, R5 is (C b H 2b+1 This shows that (b = an integer between 1 and 20). Specifically, the raw materials for component Z can include (meth)acrylate methoxypolyethylene glycol ester and (meth)acrylate methoxypolypropylene glycol ester.

[0083] <Embodiment 3> A release layer according to one embodiment of the second invention of the present invention has a normal peeling force of 50 mN / 50 mm or more and 400 mN / 50 mm or less, and a post-heating peeling force of twice or less the normal peeling force.

[0084] In this specification, normal peel strength refers to the T-shaped peel strength value measured in the following process: Adhesive tape ("31B" manufactured by Nitto Denko Corporation) is attached to the surface of the release film, and after being pressed with a pressure roller with a linear pressure of 5 kgf / mm, it is left for 20 hours under conditions of 22°C and 60% humidity. The release film with the adhesive tape attached is shredded into strips 25 mm wide and 150 mm long. One end of the adhesive tape is fixed, and one end of the release film is supported, and the release film side is pulled at a speed of 300 mm / min to peel it off, and the T-shaped peel strength is measured. A tensile testing machine ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) is used to measure the T-shaped peel strength.

[0085] In this specification, the post-heating peel strength refers to the T-shaped peel strength value measured in the following process: Adhesive tape (manufactured by Nitto Denko Corporation, product name "31B") is attached to the surface of the release film, and after being pressed with a pressure roller with a linear pressure of 5 kgf / mm, the release film with the adhesive tape attached is cut into strips 25 mm wide and 150 mm long, and heated in an oven at 70°C for 20 hours. Then, one end of the adhesive tape is fixed, one end of the release film is grasped, and the release film side is pulled at a speed of 300 mm / min to peel it off, and the T-shaped peel strength is measured. A tensile testing machine ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) is used to measure the T-shaped peel strength.

[0086] The aforementioned release agent has a normal release force of 50 mN / 50 mm to 400 mN / 50 mm, and therefore exhibits mild release properties. The normal release force is preferably 50 mN / 50 mm to 300 mN / 50 mm, and more preferably 50 mN / 50 mm to 250 mN / 50 mm.

[0087] The release layer has a release force after heating that is less than twice the release force under normal conditions, and therefore retains slight release properties even after heating. A release force after heating is preferably 800 mN / 50 mm or less. Furthermore, a release force after heating is usually preferably 50 mN / 50 mm or more. A release force after heating is preferably 1.7 times or less than the release force under normal conditions, more preferably 1.5 times or less, and even more preferably 1.3 times or less. A ratio of release force after heating to release force under normal conditions that is close to 1 is particularly preferable, but it may be less than 1. The lower limit obtained to date is approximately 0.8 times.

[0088] The aforementioned release layer has a surface free energy of 30 mJ / m 2 More than 60mJ / m 2 The following is preferable. According to this, the release layer has good wettability with the material to be released. The surface free energy is 40 mJ / m 2 More than 60mJ / m 2 The following is preferable: 50 mJ / m 2 More than 60mJ / m 2 The following are even more preferable.

[0089] In this specification, surface free energy is defined as the contact angles θw and θy of water and methylene iodide (CH2I2) in contact with the release layer surface, measured using a contact angle meter (FACE Contact Angle Meter CA-X, manufactured by Kyowa Interface Science Co., Ltd.) under conditions of 20°C and 65% RH, and then calculated from these measurements according to the method described in Journal of Applied Polymer Science, vol.13, pp. 1741-1747 (1969), γ sh (Hydrogen bonding force component term) and γ sd The (hydrogen dispersion force component term) is calculated, and the sum of each component is the surface free energy γ s This is the value calculated as follows: Specifically, the hydrogen bonding force component term γ in surface energy.sh And, the hydrogen dispersion force component term γ in the surface energy of polyester film sd This refers to the contact angle θw of water with respect to the release layer surface, and the contact angle θ of methylene iodide (CH2I2). y from, 1 + cosθ w =[2×(γ sd ) 1 / 2 ×{(γ wd ) 1 / 2 / γ w}]+[2×(γ sh ) 1 / 2 ×{(γ wh ) 1 / 2 / γ w}]...Formula (A) 1 + cosθ y =[2×(γ sd ) 1 / 2 ×{(γ yd ) 1 / 2 / γ y}]+[2×(γ sh ) 1 / 2 ×{(γ yh ) 1 / 2 / γ y}]...Formula (B) It can be found by solving the following two simultaneous equations. Note that γ in the above equation w gamma y These are the surface tensions of water and methylene iodide (CH2I2), respectively, and γ wd gamma yd γ is the dispersion force component term in each surface tension. wh gamma yh γ represents the hydrogen bonding force component term at each surface tension. w =γ wd +γ wh gamma y =γ yd +γ yh Specifically, from the surface tension of water, γ w = 72.8 mJ / m 2 gamma wd = 21.8 mJ / m 2 gamma wh = 51.0 mJ / m 2 From the surface tension of methylene iodide, γ y = 50.8 mJ / m 2 gammayd = 48.5 mJ / m 2 gamma yh = 2.3 mJ / m 2 Substitute γ sd gamma sh We seek.

[0090] In a release layer according to one embodiment of the present invention, the release layer is preferably formed by crosslinking a polymer containing component X represented by the following formula (4), component Y represented by the following formula (5), and component Z represented by the following formula (6).

[0091] [ka]

[0092] In equation (4), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3.

[0093] [ka]

[0094] In equation (5), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0095] [ka]

[0096] In equation (6), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 5 and 30), R4 is H or CH3, R5 is (C b H 2b+1 This shows that (b = an integer between 1 and 20). In formula (4) representing component X, R1 is an alkyl group with 8 to 20 carbon atoms (n). If the number of carbon atoms (n) is 7 or less, component X loses its release properties and becomes sticky. On the other hand, if the number of carbon atoms (n) is 21 or more, the flexibility of component X is impaired, and the wettability of the release layer film surface becomes insufficient. The number of carbon atoms (n) is preferably 10 to 18, and more preferably 12 to 16. Furthermore, R1 may be linear or branched. Note that a linear R1 is preferred because it tends to make the release layer easier to peel off.

[0097] In formula (4) representing component X, R4 is either H or CH3, and both are preferred. As the raw material for component X, the monomer shown in the following formula (10) can be used.

[0098] [ka]

[0099] In equation (10), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3. Specifically, lauryl (meth)acrylate and stearyl (meth)acrylate can be used as raw materials for component X.

[0100] In R2 of formula (5) representing the Y component, the number of carbon atoms m is between 1 and 10. If the number of carbon atoms is 11 or more, the crosslinking density becomes sparse, the cohesive force of the release layer itself weakens, and the peeling force becomes heavier. The number of carbon atoms m is preferably between 2 and 8, and more preferably between 2 and 4.

[0101] In formula (5) representing the Y component, R4 is either H or CH3, and both are preferred. As the raw material for component Y, the monomer shown in the following formula (11) can be used.

[0102] [ka]

[0103] In equation (11), R2 is (C m H 2m OH) (m = an integer between 1 and 10) or H, R4 represents H or CH3).

[0104] Specifically, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc., can be used as raw materials for component Y.

[0105] In formula (6) representing the Z component, q is preferably between 5 and 30 in R3. If q is 4 or less, the peeling force after heating becomes heavy. On the other hand, if q is 31 or more, the long-chain alkyl group of the X component that exhibits release properties becomes less likely to be exposed at the air interface, which may lead to excessive peeling. A value of q between 6 and 25 is even more preferable.

[0106] In formula (6) representing the Z component, R3 is preferably an integer between 1 and 4. If a is 5 or greater, the hydrophobicity increases, which may worsen the wettability. A value of a between 2 and 4 is even more preferable.

[0107] In R5 of equation (6) representing the Z component, b is preferably an integer between 1 and 20. If b is 21 or greater, the hydrophilic portion of the Z component may not be easily exposed on the surface, resulting in insufficient wettability. A value of b between 1 and 10 is even more preferable.

[0108] As the raw material for component Z, the monomer shown in the following formula (12) can be used.

[0109] [ka]

[0110] In equation (12), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 5 and 30), R4 is H or CH3, R5 is (C b H2b+1 This shows that (b = an integer between 1 and 20). Specifically, the raw materials for component Z can include (meth)acrylate methoxypolyethylene glycol ester and (meth)acrylate methoxypolybutylene glycol ester.

[0111] The polymer preferably has a weight-average molecular weight of 5,000 or more and 150,000 or less. In this specification, the weight-average molecular weight is the value calculated using GPC (Gravity Propagation) to represent the weight-average molecular weight on a polystyrene basis. If the weight-average molecular weight of the polymer is less than 5,000, the entanglement between polymer chains is weak, resulting in a weak film strength when the release layer is molded, which may cause problems in post-processing steps such as the release layer detaching due to friction. On the other hand, if the weight-average molecular weight of the polymer exceeds 150,000, the viscosity of the polymer increases, making it difficult to mold the release layer. The weight-average molecular weight of the polymer is more preferably 20,000 or more and 120,000 or less.

[0112] The hydroxyl value of the polymer is preferably 1 mg KOH / g or more and 50 mg KOH / g or less. If the hydroxyl value of the polymer is less than 1 mg KOH / g, there are few functional groups that can be crosslinked by the crosslinking agent, and the release layer does not harden. If the hydroxyl value of the polymer exceeds 50 mg KOH / g, the release properties are impaired due to hydrogen bonding of the hydroxyl groups. The hydroxyl value of the polymer is more preferably 10 mg KOH / g or more and 50 mg KOH / g or less.

[0113] The polymer is preferably crosslinked with a crosslinking agent. Suitable crosslinking agents include polyisocyanates, melamines, epoxy, aluminum chelates, titanium chelates, UV-curable resins, or mixtures of two or more of these. Among these, polyisocyanates are preferred because they can be reacted under mild conditions. Crosslinking with aluminum chelates or titanium chelates may be undesirable depending on the application due to the presence of metal components. The amount of crosslinking agent added relative to the total amount of polymer raw materials is preferably 0.5% to 10% by mass, and more preferably 1% to 3% by mass.

[0114] The polymer preferably contains 1 mole to 30 moles of component Y and 1 mole to 30 moles of component Z per 100 moles of component X. This results in a polymer with good wettability and easy peeling. It is even more preferable that the amounts of components X, Y, and Z in the polymer be 10 moles to 25 moles of component Y and 5 moles to 25 moles of component Z per 100 moles of component X.

[0115] <Embodiment 4> A molded article according to one embodiment of the first and second embodiments of the present invention comprises a base material and a release layer disposed on the surface of the base material. As the release layer, one described in Embodiment 1, Embodiment 2, or Embodiment 3 can be used. When an object to be released is placed on the release layer of the molded article, the object to be released can be molded into the shape of the base material. Furthermore, since the release layer and the object to be released are easily separated, the shape of the object to be released can be maintained in a desired shape. The release layer may be disposed on one surface of the base material or on both surfaces.

[0116] As the base material, known base materials can be used. For example, resin films made of polyester such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene, and polyimides can be used as the base material.

[0117] The thickness of the base material is preferably 10 μm to 100 μm, and more preferably 25 μm to 50 μm. If the thickness of the base material is less than 10 μm, it is undesirable because it is easily deformed by heat during base material production, processing, and molding. On the other hand, if the thickness of the base material exceeds 100 μm, the amount of base material to be discarded after use increases, which is undesirable because it increases the environmental burden.

[0118] The thickness of the release layer is preferably 0.01 μm or more and 10 μm or less, and more preferably 0.05 μm or more and 1 μm or less. If the thickness of the release layer is less than 0.01 μm, it is difficult to form the release layer uniformly, and the release force may become unstable. On the other hand, if the thickness of the release layer exceeds 10 μm, the proportion of recycled material used will be low, which is uneconomical and therefore undesirable.

[0119] A coating for improved adhesion may be placed between the substrate and the release layer. Additionally, a coating for improved slipperiness and heat resistance may be placed on the surface of the substrate opposite to the surface where the release layer is placed.

[0120] The method for forming a release layer on the surface of the substrate is not particularly limited. For example, a release agent containing the raw materials for the release layer is dissolved or dispersed in a solvent such as toluene to obtain a coating solution. This coating solution is then applied to the surface of the substrate. Subsequently, the solvent is dried off the applied coating solution, and then the raw materials are cured by heating and ultraviolet irradiation. The conditions for thermal curing of the raw materials and drying off the solvent should be appropriately selected to ensure a rapid reaction, depending on the type of raw materials, the thickness of the release layer, and the size of the substrate.

[0121] The molded product can be used, for example, as a release sheet for molding semiconductor packages, tape for electronic materials, ceramic sheets, resin sheets and electrode sheets, and carrier sheets for manufacturing circuit boards, etc.

[0122] <Embodiment 5> A mold release agent according to one embodiment of the first invention of the present invention comprises a polymer containing component X represented by the following formula (1) and component Y represented by the following formula (2), and a crosslinking agent.

[0123] [ka]

[0124] In equation (1), R1 is (C n H 2n+1)(n=an integer between 8 and 20), R4 represents H or CH3.

[0125] [ka]

[0126] In equation (2), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0127] The X and Y components are the same as those described in Embodiment 1. The release agent preferably contains 1 mole to 30 moles of Y component per 100 moles of X component, and more preferably 5 moles to 25 moles. In addition to the X and Y components, the release agent may also contain the Z component described in Embodiment 2. In this case, the release agent preferably contains 1 mole to 30 moles of Y component and 1 mole to 30 moles of Z component per 100 moles of X component.

[0128] The crosslinking agent is the same as the crosslinking agent described in Embodiment 1. The crosslinking agent is preferably included in an amount of 0.1% to 10% by mass, and more preferably in an amount of 0.5% to 3% by mass, relative to the total amount of polymer raw materials.

[0129] To form a release layer from the aforementioned release agent, for example, the following steps are performed: A coating solution in which the release agent is dissolved or dispersed in a solvent such as toluene is applied to the surface of the substrate. The amount of solid components of the release agent is preferably 0.1% to 5% by mass of the solvent. Subsequently, after drying and removing the solvent from the applied coating solution, a release layer can be formed on the substrate by heating and / or ultraviolet irradiation to cause a crosslinking reaction of the raw material resin.

[0130] <Embodiment 6> A mold release agent according to one embodiment of the present invention comprises a polymer containing component X represented by the following formula (4), component Y represented by the following formula (5), and component Z represented by the following formula (6), and a crosslinking agent.

[0131] [ka]

[0132] In equation (4), R1 is (C n H 2n+1 )(n=an integer between 8 and 20), R4 represents H or CH3.

[0133] [ka]

[0134] In equation (5), R2 is (C m H 2m OH)(m=an integer between 1 and 10) or H, R4 represents H or CH3.

[0135] [ka]

[0136] In equation (6), R3 is (C a H 2a O) q (a = integer between 1 and 4, q = integer between 5 and 30), R4 is H or CH3, R5 is (C b H 2b+1 This shows that (b = an integer between 1 and 20).

[0137] The components X, Y, and Z are the same as those described in Embodiment 3. The release agent preferably contains 1 mole to 30 moles of component Y and 1 mole to 30 moles of component Z per 100 moles of component X.

[0138] The crosslinking agent is the same as the crosslinking agent described in Embodiment 3. The release agent is preferably included in an amount of 0.5% by mass or more and 10% by mass or less, relative to the total amount of polymer raw materials, and more preferably in an amount of 1% by mass or more and 3% by mass or less.

[0139] To form a release layer from the aforementioned release agent, for example, the following steps are performed: A coating solution in which the release agent is dissolved or dispersed in a solvent such as toluene is applied to the surface of the substrate. The amount of solid components of the release agent is preferably 0.1% to 5% by mass of the solvent. Subsequently, after drying and removing the solvent from the applied coating solution, the raw material resin is cured by heating and / or ultraviolet irradiation, thereby forming a release layer on the substrate. [Examples]

[0140] The present invention will be described in more detail by reference to examples. However, the present invention is not limited by these examples.

[0141] <First Invention: Samples 1-21, Second Invention: Samples 22-26> (Preparation of release agent polymer and release layer coating liquid) According to the mixing ratios described in Table 1 (First Invention) and Table 2 (Second Invention), component X raw material (using a linear R1 in formulas (7) and (10) above), component Y raw material, and component Z raw material were mixed, toluene was added to achieve a solid content concentration of 40% by weight, and copolymerization was carried out under a nitrogen atmosphere by adding 0.5 mol% of azobisisobutyronitrile (AIBN) to obtain a polymer for mold release.

[0142] A solvent (toluene / MEK = 50 / 50: mass ratio) was added to the release agent polymer to obtain a solid content concentration of 1.0% by mass. To this, trimethylolpropane adduct of tolylene diisocyanate (manufactured by Tosoh Corporation, Coronate L, concentration 75% by mass) was added as a crosslinking agent in the amounts shown in Tables 1 and 2 for 100 parts by weight of the solid content of the release agent, and 0.1 parts by weight of organotin (manufactured by Nitto Chemical Industries, Ltd., Neostan® U-860) was added as a catalyst to obtain a release layer coating liquid.

[0143] (Formation of release layer) The obtained release layer coating solution was applied to the corona-treated surface of a polyethylene terephthalate film (Toyobo Co., Ltd., E5100) using a gravure coater, and then dried at 140°C for 1 minute to form a release layer with a thickness of 0.1 μm.

[0144] <Measurement> (Weight average molecular weight) The weight-average molecular weight of the obtained release agent polymer was calculated using GPC to obtain the weight-average molecular weight in terms of polystyrene. The results are shown in Table 1 or Table 2.

[0145] (Hydroxyl value) The hydroxyl value of the obtained release agent polymer was measured in accordance with JIS K0070-1992. The results are shown in Table 1 or Table 2.

[0146] <Rating> (Surface free energy) Using a contact angle meter (FACE Contact Angle Meter CA-X manufactured by Kyowa Interface Science Co., Ltd.), the contact angle θ between water and methylene iodide in contact with the release surface was measured under conditions of 22°C and 60% RH. w and θ y Measure and from these measurements, γ according to the method described in Journal of Applied Polymer Science, vol.13, pp. 1741-1747 (1969) sh (Hydrogen bonding force component term) and γ sd The (hydrogen dispersion force component term) is calculated, and the sum of each component is the surface free energy γ s The calculation was performed as follows: A higher surface free energy indicates better wettability. The results are shown in Table 1 or Table 2.

[0147] (Normal peeling force) Adhesive tape ("31B" manufactured by Nitto Denko Corporation) was bonded to the surface of the release film, and after being pressed with a pressure roller with a linear pressure of 5 kgf / mm, it was left for 20 hours under conditions of 22°C and 60% humidity. The release film with the adhesive tape bonded to it was cut into strips 25 mm wide and 150 mm long. One end of the adhesive tape was fixed, and one end of the release film was supported. The release film side was pulled at a speed of 300 mm / min, and the T-shaped peel strength was measured. A tensile tester ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) was used for the measurement. The results are shown in Table 1 or Table 2.

[0148] (Peeling force after heating) Adhesive tape (manufactured by Nitto Denko Corporation, product name "31B") was applied to the surface of the release film, and after being pressed with a pressure roller with a linear pressure of 5 kgf / mm, the release film with the adhesive tape applied was cut into strips 25 mm wide and 150 mm long, and heated in an oven at 70°C for 20 hours. Then, one end of the adhesive tape was fixed, and one end of the release film was grasped, and the release film side was pulled at a speed of 300 mm / min to peel it off, and the T-shaped peel strength was measured. A tensile tester ("AUTOGRAPHAG-X" manufactured by Shimadzu Corporation) was used to measure the T-shaped peel strength. The results are shown in Table 1 or Table 2.

[0149] [Table 1]

[0150] <Evaluation Results> The release layer of samples 1 to 17 has a surface free energy of 30 mJ / m². 2 More than 60mJ / m 2 The normal peeling force was in the range of 50 mN / 50 mm to 400 mN / 50 mm. In particular, samples 5 to 9 contained a Z component in the polymer and exhibited good wettability.

[0151] The release layers of samples 18 to 21 had a normal release force of 425 mN / 50 mm or more, indicating excessive release force. The release layer of sample 19 had a surface free energy of 21.8 mJ / m 2Therefore, the wettability was insufficient.

[0152] [Table 2]

[0153] <Evaluation Results> The release layers of samples 22 to 25 had a normal release force of 156.0 mN / 50 mm to 202.3 mN / 50 mm, and the difference between the normal release force and the release force after heating was 40.8 mN / 50 mm or less, indicating that the release force before and after heating was light. Furthermore, the surface free energy was 49.0 mJ / m². 2 More than 57.1mJ / m 2 The following range was observed, indicating good wettability.

[0154] The release layer of sample 26 had a normal release force of 177.4 mN / 50 mm, and the difference between the normal release force and the release force after heating was 343.7 mN / 50 mm, indicating that the release force after heating was heavier.

[0155] The embodiments and examples disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the present invention is indicated by the claims rather than the embodiments described above, and all modifications within the scope of the claims are intended to be included in the meaning of equivalents and within the scope. [Industrial applicability]

[0156] The release layer of the present invention can be suitably used in applications such as electronic component manufacturing processes where the use of silicone release agents is difficult.

Claims

1. A molded body comprising a base material and a release layer disposed on the surface of the base material, The aforementioned release layer is Surface free energy is 30 mJ / m ２ 60mJ / m or more ２ The release layer is as follows: The aforementioned release layer is formed by crosslinking a polymer consisting of component X represented by the following formula (1) and component Y represented by the following formula (2). The polymer has a weight-average molecular weight of 5,000 or more and 150,000 or less. The polymer contains 1 mole to 30 moles of component Y per 100 moles of component X. R in equation (1) which represents the X component １ It does not contain any components with 7 or fewer carbon atoms (n). The aforementioned polymer satisfies at least one of the following conditions regarding the amount of component Y or the polymer hydroxyl value: The polymer contains 10 moles or more and 25 moles or less of component Y per 100 moles of component X, or The hydroxyl value of the polymer is 10 mg KOH / g or more and 50 mg KOH / g or less. The molded body is one type of molded body selected from a release sheet for molding semiconductor packages, a carrier sheet for manufacturing ceramic sheets, a carrier sheet for manufacturing electrode sheets, or a carrier sheet for manufacturing circuit boards; 【Chemistry 1】 (In formula (1), R １ is (C ｎ H ２ｎ＋１ ) (n = an integer between 8 and 16, excluding n = 16), R ４ (This indicates H) 【Chemistry 2】 (In formula (2), R ２ is (C ｍ H ２ｍ OH) (an integer where m = 1 or more and 10 or less) or H, R ４ indicates H).

2. The molded article according to claim 1, wherein the release layer contains a crosslinking agent in an amount of 0.1% by mass or more and 10% by mass with respect to 100 parts by weight of the polymer.

3. The normal peeling force of the release layer is 50 mN / 50 mm or more and 400 mN / 50 mm or less. The molded article according to claim 1, wherein the thickness of the substrate is 10 μm or more and 100 μm or less.

4. In formula (1) above, R １ The molded article according to claim 1, wherein the elements are linear.

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