Film and semiconductor package

Abstract

The present invention provides a film having a low coefficient of linear expansion. A film according to the present invention contains an organopolysiloxane, and the signal intensity of the free induction decay associated with spin-spin relaxation of all protons at room temperature was measured for the film using the CPMG technique for solid state NMR, a fitting process according to formula (I) was performed using the signal intensity, and among three components A, B, and C, in order of shortest relaxation time, the relaxation time T2c of the component C was 2.0 milliseconds or less.

Description

Films, semiconductor packages

[0001] The present invention relates to a membrane and a semiconductor package.

[0002] The film is used, for example, as an interlayer insulating film in a semiconductor chip, and as a connection layer with a printed wiring board (for example, a build-up layer and an interposer).

[0003] For example, Patent Document 1 discloses a composition having a predetermined structure as a film material.

[0004] Japanese Patent Application Publication No. 8-143578

[0005] The present inventors have studied a film formed using a composition having the constitution as described in Patent Document 1 and have found that the linear expansion coefficient is high and there is room for improvement.

[0006] Therefore, an object of the present invention is to provide a film with a low linear expansion coefficient, and a semiconductor package.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0008] [1] A film containing an organopolysiloxane, wherein the signal intensity of the free induction decay of the spin-spin relaxation of all protons at room temperature is measured for the film by the CPMG method of solid-state NMR, and the signal intensity is used to perform a fitting process using the formula (I) described below, and the relaxation time T of the component C is determined from three components, component A, component B, and component C, in order of shortest relaxation time. ２ｃ [2] T ２ｃis 1.0 milliseconds or less. [3] The film according to [1] or [2], wherein the organopolysiloxane contains a unit represented by formula (1) described below. [4] The film according to any one of [1] to [3], wherein, when the peak area derived from a structure represented by any one of formulas (3) to (6) described below is measured by Si-NMR measurement of the film, the ratio of the peak area derived from the structure represented by formula (3) to the sum of the peak areas derived from the structures represented by any one of formulas (3) to (6) is 75% or more. [5] The film according to [3], wherein the group having a mesogenic group contains one or more rings, and the total number of monocyclic ring structures in the one or more rings is two or more. [6] The film according to [3] or [5], wherein the group having a mesogenic group has a heteroatom. [7] The film according to [3], [5], or [6], wherein the group having a mesogen group contains one or more rings, and a monocyclic ring structure in the one or more rings contains a heteroatom. [8] The film according to any one of [3] and [5] to [7], wherein the content of the organopolysiloxane containing a unit represented by formula (1) above is 50 mass% or more relative to the total mass of the film. [9] The film according to any one of [3] and [5] to [8], wherein the content of the organopolysiloxane containing a unit represented by formula (1) described below is 80 mass% or more relative to the total mass of the film.

[10] A semiconductor package comprising the film according to any one of [1] to [9].

[0009] According to the present invention, a film having a low linear expansion coefficient can be provided, and a semiconductor package can also be provided.

[0010] relaxation time T ２Ｃ FIG. 1 is a schematic diagram for explaining a measurement method.

[0011] The present invention will be described in detail below. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In addition, in the numerical ranges described in stages in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0012] Furthermore, the term "process" in this specification does not only refer to an independent process, but also includes a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] In this specification, unless otherwise specified, the temperature condition may be 25° C. For example, unless otherwise specified, the temperature when performing each step may be 25° C.

[0014] In the present specification, the bonding direction of the divalent group (for example, —O—CO—) is not particularly limited. １ｚ -L ２ｚ -L ３ｚ In the bond ２ｚ When is —O—CO—, L １ｚ The position where it is bonded to the side is *1, L ３ｚ If the position bonded to the side is *2, then L ２ｚ may be *1-O-CO-*2 or *1-CO-O-*2.

[0015] In this specification, "transparent" means that the average transmittance of visible light in the wavelength range of 400 to 700 nm is 80% or more, and preferably 90% or more. The average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[0016] In this specification, unless otherwise specified, "exposure" includes not only exposure using far ultraviolet light typified by mercury lamps, excimer lasers, extreme ultraviolet light, X-rays, EUV light, and the like, but also exposure using particle beams such as electron beams and ion beams.

[0017] In this specification, the content ratio of each repeating unit is a molar ratio unless otherwise specified.

[0018] In this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

[0019] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) is a value determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0020] In this specification, the term "solid content" refers to, for example, components that form a composition layer formed using a composition, and when the composition contains a solvent (e.g., an organic solvent, water, etc.), it refers to all components excluding the solvent. Furthermore, liquid components that form a composition layer are also considered to be solid content.

[0021] In this specification, unless otherwise specified, the thickness of a film is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and the average thickness measured using a transmission electron microscope (TEM) for thicknesses of less than 0.5 μm. The average thickness is obtained by cutting a sample to be measured using an ultramicrotome, measuring the thickness at any five points, and calculating the arithmetic average of the thicknesses.

[0022] [Membrane] The membrane of the present invention is a membrane containing an organopolysiloxane, and is characterized in that the signal intensity of the free induction decay of the spin-spin relaxation of all protons at room temperature is measured by the CPMG (Carr-Purcell-Meiboom-Gill) method of solid-state NMR (nuclear magnetic resonance analysis) for the membrane, and fitting processing is performed using the signal intensity according to formula (I), and the relaxation time T of component C is determined from three components, component A, component B, and component C, in order of shortest relaxation time. ２ｃHowever, it is 2.0 milliseconds or less.

[0023] Although the detailed mechanism of the effect of the membrane of the present invention is not clear, the present inventors speculate as follows. ２ｃ The advantage is that T is 2.0 milliseconds or less. ２ｃ When the time t is 2.0 milliseconds or less, the mobility of the organopolysiloxane in the film is particularly low, and as a result, it is presumed that the linear expansion coefficient of the film will be low. Note that, for example, when the film is disposed on a copper plate (copper wiring), the linear expansion coefficient is as low as that of the copper plate.

[0024] <T ２ｃ > T ２ｃ is 2.0 milliseconds or less. ２ｃ is preferably 1.5 milliseconds or less, and more preferably 1.0 milliseconds or less in terms of being superior in at least one of the glass transition temperature and the linear expansion coefficient. There is no particular lower limit, but it is often 0.1 milliseconds or more.

[0025] T ２ｃ As described above, is the relaxation time of component C, which has the longest relaxation time in the film measured by a predetermined method. The signal intensity of the free induction decay obtained by the above-mentioned CPMG method of solid-state NMR is fitted with formula (I) and waveform separated into three components, component A, component B and component C, in order of shortest relaxation time, to evaluate the mobility of various components contained in the film of the measurement object. For example, if the relaxation time decays slowly with the passage of echo time, it means that the mobility of various components in the film is high. Also, if the relaxation time decays rapidly with the passage of echo time, it means that the mobility of various components in the film is low. In this way, by understanding the decay trend of the relaxation time, the mobility of various components in the film can be evaluated. Here, T ２ｃ is the relaxation time of component C, and is therefore particularly suitable for evaluating highly mobile components in the object to be measured. In the present invention, an example of a highly mobile component is organopolysiloxane. ２ｃis a value that mainly reflects the mobility of the organopolysiloxane, and as described above, in the present invention, it is preferable that the mobility of the organopolysiloxane is low. ２ｃ The smaller the value, the more preferable it is.

[0026] The T obtained by the above measurement method ２ｃ If T is small, it indicates that the relaxation time of component C is short, while T ２ｃ If T is large, it indicates that the relaxation time of component C is long. ２ｃ By measuring the T ２ｃ If the time is 2.0 milliseconds or less, the mobility of the various components in the film (particularly the highly mobile component (component C)) will be low, and it is presumed that the linear expansion coefficient of the film will be low.

[0027] T ２Ｃ First, the signal intensity of the free induction decay (FID) signal of the spin-spin relaxation of all protons at room temperature (e.g., 23°C) is measured for a film to be measured by the CPMG method of solid-state NMR. Specifically, the signal intensity is measured by the CPMG method under the following conditions: pulses are repeated L times at an echo time interval of 2τ, and the FID signal after the echo time 2τ x L is measured; and the FID signal is then Fourier-transformed to obtain １ The integrated area value of the region of −10 to 20 ppm of the H MAS NMR spectrum is obtained, and this value is taken as the signal intensity (measured value).

[0028] (Measurement conditions) Pulse program: cpmg (built into Bruker's control and measurement software "TopSpin3.5") 90° pulse width: 2.6 μs 180° pulse width: 5.2 μs Echo pulse time interval τ: 40 μs Number of echo pulse irradiations: 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 30, 40, 60, 80, 100, 120 Number of accumulations: 8 times MAS rotation speed: 12 kHz Measurement temperature: room temperature (23°C)

[0029] The above measurement method is so-called pulsed NMR measurement. The solid-state NMR apparatus used for the solid-state NMR measurement is not particularly limited, but for example, Bruker AVANCE III HD 400WB / HX CP / MAS probe BL4 manufactured by Bruker Corporation can be mentioned. The resonant frequency of the solid-state NMR apparatus is preferably 400 to 700 MHz, more preferably 400 MHz. The object to be measured is T ２ｃ In order to accurately measure the NMR spectrum, the solid may be pre-treated before the solid-state NMR measurement. Examples of the pre-treatment include pulverization. Regarding detailed measurement conditions, the measurement method shown in the Examples below is preferred.

[0030] Next, the signal intensities (actually measured values) are plotted (black dots in FIG. 1) against each echo time (2τ×L) to obtain profile data. Then, the profile data is fitted with equation (I) to obtain the relaxation time T ２ｃ Specifically, using the Solver add-in of Excel (registered trademark, manufactured by Microsoft Corporation), fitting is performed so as to minimize the sum of squares of the difference between the measured value of the signal intensity and the calculated value of the signal intensity calculated from formula (I), i.e., using the least squares method, and decay curves derived from components A, B, and C in order of shortest relaxation time are obtained, and the relaxation time T ２ｃ For example, the echo time 2τL is obtained. １ , 2τL ２ and 2τL ３ The FID signals after each were measured, and the signal intensity L １ , signal strength L ２ and signal strength L ３ When the signal intensities (measured values) of the three points are plotted against each echo time (2τ × L) to obtain profile data, the signal intensity L １ and the signal intensity I calculated from equation (I) １ The square of the difference between the signal strength L １ - Signal Strength I １ ) ２ ); signal strength L ２ and the signal intensity I calculated from equation (I) ２ The square of the difference between the signal strength L ２- Signal Strength I ２ ) ２ ); signal strength L ３ and the signal intensity I calculated from equation (I) ３ The square of the difference between the signal strength L ３ - Signal Strength I ３ ) ２ Each term in formula (I) is determined so that the sum of the coefficients of determination (R) is minimized. By the above measurement method, for example, the solid line represented by formula (I) shown in Figure 1 can be obtained. The decay curve derived from components A, B, and C is fitted as an exponential function. When the three components A, B, and C cannot be fitted normally as variables (for example, when the coefficient of determination R ２ ≦0.8), a plot of the region in the profile data obtained above where the echo time is longer than 1 millisecond is fitted with a single exponential function, and the obtained relaxation time is taken as the relaxation time T ２ｃ Then, similar fitting may be performed using the A and B components as variables to obtain the relaxation times of all three components.

[0031] I=A×exp(-t / T ２ａ )+B×exp(-t / T ２ｂ )+C×exp(-t / T ２ｃ ) (I) A: Component ratio of component A T ２ａ : Relaxation time of component A B: Component ratio of component B T ２ｂ : Relaxation time of component B C: Component ratio of component C T ２ｃ : Relaxation time of component C

[0032] The component ratio of each component means the ratio (%) of each component to the total amount of component A, component B, and component C.

[0033] Components A, B, and C are components contained in the membrane, each defined by its relaxation time. Component A has the shortest relaxation time and is a component with relatively low mobility in the membrane (low mobility component), component B has the next shortest relaxation time and is a component with mobility between components A and B (intermediate mobility component), and component C has the longest relaxation time and is a component with relatively high mobility in the membrane (high mobility component).

[0034] T ２ｃAs a method for adjusting T, for example, a method using a component with low mobility can be mentioned, and it is preferable to use a suitable organopolysiloxane as described below. ２ｃ As a method for adjusting the above, a method for adjusting the above so as to satisfy at least one selected from the group consisting of requirements A to C is preferred, and a method for adjusting the above so as to satisfy requirements A and C, or requirements B and C is more preferred. Method A: A heat treatment is carried out in step X described below. Method B: The composition or composition layer contains a crosslinking agent. Method C: The organopolysiloxane or organopolysiloxane S has a group having a mesogenic structure.

[0035] <Organopolysiloxane> The film contains an organopolysiloxane. The organopolysiloxane is preferably a cured product of organopolysiloxane S described below.

[0036] Examples of the structure of the organopolysiloxane include irregular structures such as random structures, ladder structures, cage (fully condensed cage) structures, and incomplete cage structures (partially cleaved cage structures in which some silicon atoms are missing from the cage structure and some silicon-oxygen bonds are cleaved in the cage structure), with the ladder structure being preferred.

[0037] The organopolysiloxane preferably contains a unit represented by formula (1).

[0038] Formula (1) R ａ -SiO ３／２

[0039] In formula (1), R ａrepresents a group having a mesogen group. The group having a mesogen group is not particularly limited as long as it is a group having a mesogen group. A mesogen group is a group that represents the main skeleton of a liquid crystal molecule that contributes to liquid crystal formation. The liquid crystal molecule exhibits liquid crystallinity, which is an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. For mesogen groups, reference can be made to, for example, "Flussige Kristalle in Tablellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, published in 1984), particularly the description on pages 7 to 16, and "Liquid Crystal Handbook" edited by the Liquid Crystal Handbook Editorial Committee (Maruzen, published in 2000), particularly the description in Chapter 3. The mesogenic group contains one or more rings, and the ring is preferably at least one ring selected from the group consisting of aromatic rings (aromatic hydrocarbon rings and aromatic heterocyclic rings) and alicyclic rings (aliphatic heterocyclic rings and aliphatic hydrocarbon rings), and more preferably at least one ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings. Furthermore, in terms of achieving a superior glass transition temperature and linear expansion coefficient, it is preferable that the group having a mesogenic group contains one or more rings, and that the monocyclic ring structure in the one or more rings contains a heteroatom. Examples of the heteroatom include heteroatoms that may be contained in the group having a mesogenic group described below. The ring contained in the mesogenic group may have a substituent in terms of improving the degree of orientation of the mesogenic group. Examples of the substituent include -NR Ｎ -, an aryl group, an alkyl group, an alkoxy group, an alkyl ester group or an acetyl group is preferred. Ｎrepresents a hydrogen atom or an alkyl group. The aryl group is preferably a phenyl group or a naphthyl group. The ring contained in the mesogenic group may be either a monocyclic or polycyclic ring. That is, the aromatic ring and alicyclic ring may be either a monocyclic or polycyclic ring, with a monocyclic ring being preferred. The aromatic ring and alicyclic ring may also be a fused ring. The number of ring members in the aromatic hydrocarbon ring, heterocyclic ring, and alicyclic ring is preferably 5 to 12, more preferably 5 or 6. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 12, more preferably 5 or 6. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring, with a benzene ring being preferred. The number of carbon atoms in the heterocyclic ring is preferably 3 to 12, more preferably 3 to 6. Examples of aromatic heterocycles include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a thiazole ring, and a benzothiazole ring, with a thiophene ring, a pyrimidine ring, a triazine ring, or a thiazole ring being preferred. The number of carbon atoms in the alicyclic ring is preferably 6 to 12, more preferably 5 or 6. Examples of the alicyclic ring include a cycloalkane ring such as a cyclopentane ring and a cyclohexane ring. Furthermore, rings contained in the mesogenic group are preferably bonded to each other via a single bond or a divalent linking group, and more preferably bonded via a divalent linking group, for reasons such as the fact that the structure of the organopolysiloxane becomes planar. Examples of the divalent linking group include the L described below. ｘ３ Examples of the divalent linking group include a divalent linking group having no ring and represented by the following formula:

[0040] The group having a mesogenic group also preferably has a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom, with a nitrogen atom or an oxygen atom being preferred. When the group having a mesogenic group has a heteroatom, it is preferable that the group having a mesogenic group has at least one of a heteroatom as a ring member atom constituting a ring contained in the mesogenic group and a heteroatom as a group connecting the rings. Specifically, the group having a mesogenic group preferably has at least one group or ring selected from the group consisting of -COO-, -CONH-, -O-, -NH-, -N=N-, a pyrimidine ring, a triazine ring, a thiophene ring, and a thiazole ring. At least two rings selected from the above group may be fused to each other to form a fused ring. For example, a thiophene ring and a thiazole ring may be fused to form a thienothiazole ring.

[0041] The mesogenic group preferably has two or more (preferably 2 to 10) nitrogen atoms. The number of nitrogen atoms is not limited to the number of nitrogen atoms in the ring of the mesogenic group, but refers to the number of nitrogen atoms in the mesogenic group as a whole. Specifically, when the mesogenic group is a group having a "-benzene ring-N=N-triazine ring-", the number of nitrogen atoms is five, and therefore this corresponds to a preferred embodiment of the mesogenic group. Furthermore, the mesogenic group preferably has at least an aromatic heterocycle having a nitrogen atom as a ring member atom.

[0042] The group having a mesogenic group contains one or more rings, and the total number of monocyclic ring structures among the one or more rings is preferably two or more, more preferably three or more, and even more preferably four or more. The upper limit of the total number of the monocyclic ring structures is preferably 10 or less, more preferably six or less. The monocyclic ring structure refers to a ring structure such as a monocyclic aromatic hydrocarbon ring, a monocyclic heterocyclic ring, or a monocyclic alicyclic ring that the mesogenic group may have. For example, in a ring obtained by condensing two monocyclic rings, the total number of monocyclic ring structures is two. Specifically, a thienothiazole ring is a ring obtained by condensing a thiophene ring and a thiazole ring, and the total number of monocyclic ring structures is two. For example, when the group having a mesogenic group contains two benzene rings and one thienothiazole ring, the total number of monocyclic ring structures is four. It is also preferable that the group having a mesogenic group contains one or more rings, and the monocyclic ring structures among the one or more rings contain a heteroatom.

[0043] The group contained in the mesogenic group is preferably a group represented by formula (X) or a group represented by formula (Y), and more preferably a group represented by formula (X).

[0044]

[0045] In formula (X), * represents a bonding position. ｘ１ represents a ring. ｘ２ represents a single bond, —COO—, —CONH—, —O—, or —CH ２ represents O-, -N=N-, -CH=CH-, -C≡C- or -CH=N-. ｘ３ represents a single bond or a divalent linking group having no ring. ｘ represents a hydrogen atom or a substituent not having a ring. nx represents an integer of 2 or more. In formula (Y), * represents a bonding position. Ar ｙ１ ~Ar ｙ４ each independently represents a monocycle. ｙ１ ~L ｙ３ each independently represents a single bond, —COO—, —CONH—, —O—, or —CH ２ represents O—, —NH—, —N═N—, —CH═CH—, —C≡C—, or —CH═N—. ｙ４represents a single bond or a divalent linking group having no ring. ｙ１ and R ｙ２ each independently represents a hydrogen atom or a substituent not having a ring, my1 to my3 each independently represents an integer of 0 or more, and my1 + my2 + my3 represents an integer of 1 or more, provided that L ｘ１ If there are multiple L ｘ１ may be the same or different. ｘ２ If there are multiple L ｘ２ Ar may be the same or different. ｙ１ When there are multiple Ar ｙ１ Ar may be the same or different. ｙ２ When there are multiple Ar ｙ２ Ar may be the same or different. ｙ３ When there are multiple Ar ｙ３ They may be the same or different. ｙ１ If there are multiple L ｙ１ They may be the same or different. ｙ２ If there are multiple L ｙ２ They may be the same or different. ｙ３ If there are multiple L ｙ３ They may be the same or different.

[0046] L ｘ１ Examples of the ring represented by the formula (I) include one or more rings exemplified as the one or more rings contained in the mesogenic group described above, and a benzene ring, a pyrimidine ring, a triazine ring, or a thienothiazole ring is preferred. Ｘ１ The ring represented by the formula (I) constitutes a divalent group. ｘ２ is preferably a single bond, —COO—, —CONH— or —N═N—. ｘ３ Examples of the divalent linking group having no ring represented by the formula (I) include an alkylene group, -O-, -CO-, -COO-, and a group formed by combining these groups, with -alkylene group-O-, -alkylene group-CO-, or -alkylene group-COO- being preferred. The alkylene group may be linear or branched, with linear being preferred. The alkylene group preferably has 1 to 10 carbon atoms.

[0047] R ｘ Examples of the non-ring-containing substituent represented by the formula (I) include an alkyl group, an alkoxy group, an alkyl ester group, and an acetyl group. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms. ｘ is preferably a hydrogen atom.

[0048] nx is an integer of 2 or more, and the upper limit is preferably an integer of 10 or less, and more preferably an integer of 6 or less.

[0049] Ar ｙ１ ~Ar ｙ４ The monocyclic ring represented by the formula (I) may be a monocyclic ring selected from the rings exemplified as one or more rings contained in the group contained in the mesogenic group. ｙ１ ~Ar ｙ３ The ring represented by Ar ｙ４ The ring represented by L constitutes a trivalent group. ｙ１ ~L ｙ３ is preferably a single bond, —COO—, —CONH—, —NH— or —N═N—, and more preferably —COO—, —CONH—, —NH— or —N═N— for reasons such as the planar structure. ｙ４ The divalent linking group having no ring represented by the formula ｘ３ The meaning and preferred embodiments are also the same as the divalent linking group having no ring represented by the formula: ｙ１ and R ｙ２ The substituent having no ring represented by the above R ｘ The meaning and preferred embodiments are also the same as those of the substituent having no ring represented by the following formula:

[0050] my1 to my3 are integers of 0 or greater, and preferably an integer of 1 or greater. The upper limit is preferably an integer of 10 or less, more preferably an integer of 6 or less, and even more preferably an integer of 3 or less. Furthermore, my1 + my2 + my3 (the total of my1 to my3) is an integer of 1 or greater, preferably an integer of 2 or greater, more preferably an integer of 2 to 10, still more preferably an integer of 2 to 7, and particularly preferably an integer of 3 to 5.

[0051] The unit represented by formula (1) may be used alone or in combination of two or more. The content of the unit represented by formula (1) is preferably 20 mol% or more, more preferably 50 mol% or more, and even more preferably 80 mol% or more, based on the total units (100 mol%) of the organopolysiloxane. The upper limit is preferably 100 mol% or less.

[0052] The organopolysiloxane may contain a unit represented by formula (2).

[0053] Formula (2) R ｂ ２ -SiO ２／２

[0054] In formula (2), R ｂ each independently represents a hydrocarbon group or a group having a mesogenic group.

[0055] R ｂ The group having a mesogen group represented by R ａ The meaning and preferred embodiments are also the same as those of the group having a mesogen group represented by the following formula:

[0056] R ｂ The hydrocarbon group represented by may be a monocyclic aromatic hydrocarbon ring group, a monocyclic alicyclic group, or a linear or branched aliphatic hydrocarbon group. The number of ring members in the aromatic hydrocarbon ring group is preferably 5 to 12, more preferably 5 or 6. The number of carbon atoms in the aromatic hydrocarbon ring group is preferably 6 to 12, more preferably 5 or 6. As the aromatic hydrocarbon ring group, a benzene ring group (phenyl group) is preferred. As the aliphatic hydrocarbon group, a linear one is preferred. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the aliphatic hydrocarbon group include alkyl groups (e.g., methyl and ethyl groups), alkenyl groups (e.g., vinyl groups), alkynyl groups, and groups formed by combining these groups, with alkyl groups or alkenyl groups being preferred. R ｂ is preferably a group having a hydrogen atom, an alkyl group, an alkenyl group or a mesogenic group, and more preferably a hydrogen atom, a methyl group, a vinyl group or a phenyl group. ｂAt least one of R preferably represents a linear or branched hydrocarbon group, and ｂ It is more preferable that at least one of R represents an alkyl group, and ｂ More preferably, all of represent an alkyl group.

[0057] The units represented by formula (2) may be used alone or in combination of two or more. The content of the units represented by formula (2) is preferably 80 mol% or less, more preferably 50 mol% or less, based on the total units (100 mol%) of the organopolysiloxane. The lower limit is preferably 0 mol% or more.

[0058] The organopolysiloxane may contain units other than the units represented by formula (1) and the units represented by formula (2). Examples of the other units include T units other than the units represented by formula (1) and D units other than the units represented by formula (2).

[0059] The content of the unit represented by formula (1), the unit represented by formula (2), and other units is, for example, ２９ The content of each of the above units can be measured using Si-NMR (nuclear magnetic resonance analysis). ２９ The measurement may be performed using Si-NMR. ２９ The ratio of the content of the unit represented by formula (1) to the content of the unit represented by formula (2) can be calculated by calculating the ratio of the peak area appearing between −30 and 0 ppm in the Si-NMR spectrum (corresponding to the content of D units) to the peak area appearing between −80 and −30 ppm (corresponding to the content of T units).

[0060] The weight average molecular weight of the organopolysiloxane is preferably 1,000 to 1,000,000, more preferably 1,000 to 500,000, and even more preferably 2,000 to 50,000.

[0061] The method for producing organopolysiloxanes is not particularly limited, and they can be produced, for example, by hydrolytic condensation of raw materials containing monomers that will become various units, such as units represented by formula (1). As mentioned above, it is preferable that the organopolysiloxane has a ladder structure. An example of a method for producing an organopolysiloxane with a ladder structure is a method in which, when a monomer that will become a unit represented by formula (1) is hydrolytically condensed, the reaction is carried out while discharging by-products such as alcohol (e.g., methanol) generated in the system. Specifically, during the hydrolytic condensation of each of the monomers, the reaction is carried out while removing refluxed methanol from the system using a Dean-Stark apparatus.

[0062] The organopolysiloxane may be used alone or in combination of two or more. The content of the organopolysiloxane (preferably an organopolysiloxane containing a unit represented by formula (1)) is preferably 50% by mass or more relative to the total mass of the film in order to increase the glass transition temperature, and more preferably 80% by mass or more in order to decrease the linear expansion coefficient. The upper limit is preferably 100% by mass or less.

[0063] When the peak area derived from the structure represented by any one of formulas (3) to (6) is measured by Si-NMR for a film, the ratio of the peak area derived from the structure represented by formula (3) to the sum of the peak areas derived from the structure represented by formula (3) to the sum of the peak areas derived from the structure represented by formula (3) to the sum of the peak areas derived from the structure represented by formula (6) (100 × peak area derived from the structure represented by formula (3) / sum of the peak areas derived from the structure represented by formula (3) to the sum of the peak areas derived from the structure represented by formula (6)) is preferably 75% or more. Specifically, the ratio of the peak area derived from the structure represented by formula (3) is calculated by formula (X): Ratio of the peak area derived from the structure represented by formula (3) = 100 × (peak area derived from the structure represented by formula (3)) / (sum of the peak areas derived from the structure represented by formula (3) to the sum of the peak areas derived from the structure represented by formula (6)) (X) A high ratio of the peak area derived from the structure represented by formula (3) suggests that the amount of silanol groups in the organopolysiloxane is small, and it is estimated that this will result in a lower linear expansion coefficient of the film or a higher glass transition temperature of the film. Formula (3) R-SiO ３／２ Formula (4) R-Si(OH)O ２／２ Formula (5) R-Si(OH) ２ O １／２ Formula (6) R-Si(OH) ３ Each R independently represents a monovalent group.

[0064] Examples of the monovalent group represented by R include an alkyl group, an alkoxy group, an alkyl ester group, and an acetyl group. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms.

[0065] [Method for Producing Membrane] Examples of the method for producing the membrane of the present invention include known production methods. Among them, the method for producing the membrane of the first embodiment or the second embodiment is preferred.

[0066] <First embodiment> The film manufacturing method of the first embodiment includes a step X of applying a composition containing organopolysiloxane S onto a substrate to form a coating film, and curing the coating film to form a film. Examples of the substrate include the substrate in step Z1 described below.

[0067] In the step X, examples of the coating method for coating the composition on the substrate include slit coating, spin coating, curtain coating, and inkjet coating.

[0068] An example of a method for curing the coating film is a method of curing organopolysiloxane S contained in the composition. Heat treatment is preferred as a method for curing the coating film. The heating temperature is preferably 150°C or higher, more preferably 200°C or higher. The upper limit is preferably 400°C or lower. The heating time is preferably 1.0 hour or higher, more preferably 1.5 hours or higher. The upper limit is preferably 5.0 hours or lower. Furthermore, it is preferred that step X includes a heat treatment at a temperature of 150°C or higher and for a heating time of 1.5 hours or longer. By carrying out the heat treatment, organopolysiloxane S is sufficiently cured, and therefore the T of the resulting film is improved. ２ｃ is the T of the membrane of the present invention. ２ｃ It is easy to adjust within a specified range.

[0069] The coating film may be subjected to a drying treatment before the heat treatment. Furthermore, in step X, the drying treatment and the heat treatment may be performed simultaneously. The method for drying the coating film may be a known drying method, such as reduced-pressure drying, heat drying, and natural drying. The drying temperature (particularly under 1 atmosphere) is preferably 50 to 130°C, more preferably 100 to 120°C.

[0070] (Composition) -Organopolysiloxane S- The composition preferably contains organopolysiloxane S. As described above, it is preferable that the organopolysiloxane contained in the film is produced by curing the organopolysiloxane S. It is also preferable that the organopolysiloxane S is a compound that becomes the organopolysiloxane contained in the film when subjected to heat treatment. It is preferable that the organopolysiloxane S contains a structure that can be contained in the organopolysiloxane contained in the above-mentioned film (for example, a unit represented by formula (1) and a unit represented by formula (2)).

[0071] The organopolysiloxane S may have a polymerizable group. The type of the polymerizable group is not particularly limited, and examples thereof include radically polymerizable groups and cationically polymerizable groups. Examples of the radically polymerizable group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, a styryl group, and an allyl group. Examples of the cationically polymerizable group include an oxiranyl group and an oxetanyl group. The number of polymerizable groups contained in the organopolysiloxane S is not particularly limited, and may be 1 or 2 or more.

[0072] The organopolysiloxane S may be used alone or in combination of two or more. The content of organopolysiloxane S is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass or more, based on the total solid content of the composition. The upper limit is preferably 100% by mass or less.

[0073] -Crosslinking Agent- The composition preferably contains a crosslinking agent. When the composition contains a crosslinking agent, the T of the film obtained using the composition is ２ｃ is the T of the membrane of the present invention. ２ｃ In other words, the organopolysiloxane S reacts with the crosslinking agent, and the organopolysiloxane in the resulting film has crosslinked sites, which can further reduce the mobility of the organopolysiloxane. In addition, the amount of residual silanol in the organopolysiloxane in the resulting film can be easily reduced.

[0074] Examples of crosslinking agents include compounds having a group reactive with the organopolysiloxane S or a silanol group that the organopolysiloxane may have, with silicon compounds having the group reactive with the silanol group being preferred. Examples of the group reactive with the silanol group include hydrolyzable silyl groups in which a hydrolyzable group such as an alkoxy group or a ketoxime group is directly bonded to silicon (e.g., -Si-alkoxy group and -Si-ketoxime group), and silanol groups, with hydrolyzable silyl groups being preferred. The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms. The ketoxime group is preferably a dialkylketoxime group, more preferably a dialkylketoxime group having 1 to 10 carbon atoms. The number of groups reactive with the silanol group that the crosslinking agent may have is preferably 1 or more, more preferably 2 or more, and even more preferably 2 to 4.

[0075] Examples of the crosslinking agent include the following compounds.

[0076]

[0077] The content of the crosslinking agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the composition.

[0078] Polymerization Initiator The composition may contain a polymerization initiator. Examples of the polymerization initiator include thermal polymerization initiators such as peroxides, photoradical polymerization initiators, photocationic polymerization initiators, and photoanionic polymerization initiators.

[0079] Examples of peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, and peroxyesters. Specific examples include acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, t-butylcumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl triphenylperacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl per-4-methoxyacetate, and tert-butyl per-N-(3-toluyl)carbamate.

[0080] Examples of photopolymerization initiators include oxime ester compounds (photopolymerization initiators having an oxime ester structure), aminoacetophenone compounds (photopolymerization initiators having an aminoacetophenone structure), hydroxyacetophenone compounds (photopolymerization initiators having a hydroxyacetophenone structure), acylphosphine oxide compounds (photopolymerization initiators having an acylphosphine oxide structure), and bistriphenylimidazole compounds (photopolymerization initiators having a bistriphenylimidazole structure). Preferred photopolymerization initiators are oxime ester compounds or aminoacetophenone compounds. Examples of photopolymerization initiators include the photopolymerization initiators described in paragraphs 0031 to 0042 of JP 2011-095716 A and paragraphs 0064 to 0081 of JP 2015-014783 A.

[0081] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 2.0% by mass or less, based on the total solid content of the composition. The lower limit is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the composition.

[0082] -Solvent- The composition may contain a solvent. The solvent is not particularly limited as long as it can dissolve or disperse various components that may be contained in the composition other than the solvent. Examples of the solvent include water, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol, ethanol, etc.), ketone solvents (e.g., acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (e.g., toluene, etc.), aprotic polar solvents (e.g., dimethyl sulfoxide, sulfolane, etc.), amide solvents, cyclic ether solvents (e.g., tetrahydrofuran, etc.), ester solvents (e.g., n-propyl acetate, etc.), amide solvents (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, etc.), lactone solvents, and mixed solvents containing two or more of these.

[0083] -Additives- The composition may contain additives other than the various components described above. Examples of additives include crosslinking reaction catalysts, heterocyclic compounds (e.g., triazole, benzotriazole, tetrazole, and derivatives thereof, rust inhibitors), surfactants, fillers, aliphatic thiol compounds, polymerization inhibitors, hydrogen donor compounds, impurities, plasticizers, sensitizers, and polymerizable compounds. Examples of heterocyclic compounds, aliphatic thiol compounds, polymerization inhibitors, and hydrogen donor compounds include the various components described in WO 2022 / 039027. Examples of plasticizers and sensitizers include the various components described in paragraphs 0097 to 0119 of WO 2018 / 179640.

[0084] Examples of the filler include organic fillers and inorganic fillers. Examples of the filler include silicon dioxide (silica), silicates such as kaolinite, kaolin clay, calcined clay, talc, and glass fillers such as chion-doped glass, alumina, barium sulfate, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, cordierite, zirconium tungstate, and manganese nitride.

[0085] <Second Embodiment> A method for producing a film according to a second embodiment includes a step Y1 of forming a composition layer on a substrate using a transfer film having a temporary support and a composition layer containing organopolysiloxane S, and a step Y2 of curing the composition layer to form a film.

[0086] An example of the process Y1 is the method of the process Z1 described below. An example of the substrate is the substrate in the process Z1 described below. An example of the curing method in the process Y2 is the curing method in the process X described above.

[0087] (Transfer Film) The transfer film has a temporary support and a composition layer.

[0088] -Temporary Support- The transfer film includes a temporary support, which is a member that supports the composition layer and is ultimately removed by a peeling treatment.

[0089] The temporary support may have either a single-layer structure or a multi-layer structure. The temporary support is preferably a film, more preferably a resin film. The temporary support is also preferably a film that is flexible and does not significantly deform, shrink, or stretch under pressure, or under pressure and heat. Examples of the film include polyethylene terephthalate films (e.g., biaxially oriented polyethylene terephthalate films), polymethyl methacrylate films, cellulose triacetate films, polystyrene films, polyimide films, and polycarbonate films, with polyethylene terephthalate films being preferred. It is also preferable that the temporary support is free of deformations such as wrinkles and scratches.

[0090] The temporary support preferably has high transparency in order to enable pattern exposure through the temporary support. Specifically, the transmittance at each of the wavelengths of 313 nm, 365 nm, 405 nm, and 436 nm is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. The upper limit is preferably less than 100%. Preferred values ​​of the transmittance at each of the above wavelengths include, for example, 87%, 92%, and 98%. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the haze of the temporary support is preferably small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. The lower limit is preferably 0% or more. In terms of the pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, the number of fine particles, foreign matter, and defects contained in the temporary support is preferably small. Specifically, the number of particles, foreign matter, and defects with a diameter of 1 μm or more on the temporary support is 50 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 3 or less per mm ２ More preferably, 0 pieces / mm ２ As a specific example of the number of fine particles, foreign matter and defects having a diameter of 1 μm or more on the temporary support, 2 particles / mm ２ , and 0 pieces / mm ２ Examples include:

[0091] The thickness of the temporary support is preferably 5 to 200 μm, and from the viewpoint of ease of handling and versatility, more preferably 5 to 150 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 35 μm.

[0092] In order to improve the adhesion between the temporary support and the composition layer, the surface of the temporary support that comes into contact with the composition layer may be surface-modified by UV irradiation, corona discharge, plasma, etc. When the surface is modified by UV irradiation, the exposure dose of UV irradiation is 10 to 2000 mJ / cm. ２ is preferred, and 50 to 1000 mJ / cm ２ Examples of light sources for UV irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and light-emitting diodes that emit light in the wavelength range of 150 to 450 nm. The lamp output and illuminance can be adjusted as appropriate.

[0093] Examples of the temporary support include a biaxially oriented polyethylene terephthalate film having a thickness of 16 μm, a biaxially oriented polyethylene terephthalate film having a thickness of 12 μm, and a biaxially oriented polyethylene terephthalate film having a thickness of 9 μm. The temporary support may be a recycled product. Examples of the recycled product include a film obtained by cleaning and chipping used films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0094] Examples of the temporary support include those described in paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019 to 0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO 2012 / 081680, and paragraphs 0029 to 0040 of WO 2018 / 179370, the contents of which are incorporated herein by reference.

[0095] The temporary support may have a layer containing fine particles (lubricant layer) on one or both sides of the temporary support in order to provide handleability. The diameter of the fine particles contained in the lubricant layer is preferably 0.05 to 0.8 μm. The thickness of the lubricant layer is preferably 0.05 to 1.0 μm. Commercially available temporary supports include Lumirror 16FB40, Lumirror 16KS40, Lumirror #38-U48, Lumirror #75-U34, and Lumirror #25T60 (all manufactured by Toray Industries, Inc.); and Cosmoshine A4100, Cosmoshine A4160, Cosmoshine A4300, Cosmoshine A4360, and Cosmoshine A8300 (all manufactured by Toyobo Co., Ltd.).

[0096] -Composition Layer- The transfer film has a composition layer containing organopolysiloxane S. The transfer film preferably has a composition layer disposed on a temporary support. Examples of the organopolysiloxane S contained in the composition layer include the organopolysiloxane S contained in the above-described composition. Examples of various components other than organopolysiloxane S that the composition layer may contain include various components other than the solvent among the various components that the above-described composition may contain.

[0097] The average thickness of the composition layer is preferably from 0.5 to 100 μm, more preferably from 1 to 70 μm, and even more preferably from 10 to 50 μm.

[0098] - Intermediate layer and thermoplastic resin layer - The transfer film may have an intermediate layer or a thermoplastic resin layer. Examples of the intermediate layer and the thermoplastic resin layer include the intermediate layer and the thermoplastic resin layer described in paragraphs 0164 to 0204 of WO 2021 / 166719, the contents of which are incorporated herein by reference.

[0099] -Cover Film- The transfer film may have a cover film. When the transfer film includes a cover film, the cover film is preferably provided as the outermost layer on the side opposite to the temporary support. The number of fisheyes having a diameter of 80 μm or more contained in the cover film is 5 / m. ２ Preferably, 0 pieces / m ２The fisheyes are foreign matter, unmelted matter, and / or oxidized and deteriorated matter of the material that is trapped in the cover film when the cover film is produced by thermally melting the material and then kneading, extrusion and / or biaxial stretching, casting, or other methods.

[0100] The number of particles with a diameter of 3 μm or more contained in the cover film is 30 / mm ２ Preferably, 10 pieces / mm or less ２ More preferably, 5 or less pieces / mm ２ More preferably, 0 pieces / mm ２ This makes it possible to suppress defects caused by the transfer of irregularities caused by particles contained in the cover film to the composition layer.

[0101] The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 μm or more, more preferably 0.02 μm or more, and even more preferably 0.03 μm or more.If Ra is within the above range, for example, when the transfer film is long, the winding property of the transfer film is excellent.In addition, from the viewpoint of suppressing defects during transfer, the upper limit is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

[0102] Examples of the cover film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film. Examples of the cover film include the cover films described in paragraphs 0083 to 0087 and 0093 of JP 2006-259138 A, the contents of which are incorporated herein by reference.

[0103] Examples of cover films include Alphan (registered trademark) FG-201 (manufactured by Oji F-Tex Co., Ltd.), Alphan (registered trademark) E-201F (manufactured by Oji F-Tex Co., Ltd.), Therapeel (registered trademark) 25WZ (manufactured by Toray Advanced Film Co., Ltd.), and Lumirror (registered trademark) 16QS62 (16KS40) (manufactured by Toray Industries, Inc.). The cover film may be a recycled product. Examples of recycled products include those obtained by cleaning and chipping used films and then forming the resulting material into films. Examples of commercially available recycled products include the Ecouse series (manufactured by Toray Industries, Inc.).

[0104] -Other Layers- The transfer film may have other layers in addition to the above layers. Examples of the other layers include a high refractive index layer. Examples of high refractive index layers include those described in paragraphs 0168 to 0188 of WO 2021 / 187549, the contents of which are incorporated herein by reference.

[0105] [Uses] The film of the present invention can be used in a variety of applications. For example, it can be used as an electrode protective film, an insulating film, a planarizing film, an overcoat film, a hard coat film, a passivation film, a partition wall, a spacer, a microlens, an optical filter, an anti-reflection film, an etching resist, and a plated member. Specific examples include a protective film or insulating film for a touch panel electrode, a protective film or insulating film for a printed wiring board, a protective film or insulating film for a TFT substrate, an interlayer insulating film in a build-up substrate for a semiconductor package, an organic interposer, a color filter, an overcoat film for a color filter, and an etching resist for forming wiring.

[0106] [Method for Manufacturing Semiconductor Package] The method for manufacturing a semiconductor package is not particularly limited as long as it uses the above-mentioned composition or transfer film. Examples of the method for manufacturing a semiconductor package include known manufacturing methods such as manufacturing methods for build-up substrates. A manufacturing method including steps Z1 and Z2 is preferred, and a manufacturing method including steps Z1 to Z4 is more preferred. Step Z1: Forming a composition layer on a substrate using a transfer film; Step Z2: Forming a pattern having vias in the composition layer; Step Z3: Heating or exposing the pattern; Step Z4: Forming a circuit pattern on the obtained pattern. Furthermore, the method for manufacturing a laminate is a manufacturing method including steps Z1 to Z4, and preferably further includes step Z5 of forming a composition layer on the semiconductor package manufactured by step Z4 using a transfer film, and steps Z2 to Z5 are repeatedly performed.

[0107] <Step Z1> Step Z1 is a step of forming a composition layer on a substrate using a transfer film. Step Z1 is preferably a step of bringing the surface of the composition layer in the transfer film opposite the temporary support side into contact with the substrate, thereby laminating the transfer film and the substrate. Examples of methods for laminating the transfer film include known transfer methods and methods using known laminators such as laminators, vacuum laminators, and auto-cut laminators, and methods involving pressure and heat application using rolls or the like are preferred. The lamination temperature is preferably 70 to 130°C. Furthermore, when the transfer film has a cover film, step Z1 is preferably performed after peeling the cover film from the transfer film.

[0108] (Substrate) Examples of the substrate include a glass substrate, a glass epoxy substrate, a silicon substrate, a resin substrate, and a substrate having a conductive layer, with a substrate having a conductive layer being preferred. The substrate may be composed of a light-transmitting substrate such as a glass substrate, or may be tempered glass such as Corning Gorilla Glass. Examples of materials contained in the substrate include materials described in JP 2010-086684 A, JP 2010-152809 A, and JP 2010-257492 A. Resin substrates are preferably resin films with low optical distortion and / or high transparency. Specific examples include polyester, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and polyimide.

[0109] The substrate having a conductive layer is preferably a resin substrate having a conductive layer, and more preferably a resin film having a conductive layer, because it can be produced by a roll-to-roll process. The substrate having a conductive layer may also be a laminate obtained by the above-mentioned method for producing a laminate.

[0110] Examples of the conductive layer include known conductive layers used for circuit wiring or touch panel wiring. From the viewpoints of conductivity and fine line formability, the conductive layer is preferably one or more layers selected from the group consisting of a metal layer (e.g., metal foil, etc.), a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, more preferably a metal layer, and even more preferably a copper layer or a silver layer. The conductive layer may also be one or more layers. The conductive layer may be used alone or in combination of two or more types. Examples of materials for the conductive layer include simple metals and conductive metal oxides. Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of conductive metal oxides include ITO (indium tin oxide), IZO (indium zinc oxide), and SiO ２ The conductivity is such that the volume resistivity is 1×10 ６ It means that the volume resistivity is less than 1×10 ４It is preferably less than Ωcm.

[0111] The conductive layer may be patterned. Examples of methods for producing a patterned conductive layer include subtractive methods such as etching and additive methods. Examples of etching methods include wet etching methods described in paragraphs 0048 to 0054 of JP 2010-152155 A and known dry etching methods such as plasma etching. The etching method may also be a method using an etching resist.

[0112] <Step Z2> Step Z2 is a step of forming a pattern having vias in the composition layer. The pattern having vias may be formed only in the composition layer, or may be formed in both the composition layer and the substrate. Examples of methods for forming the pattern having vias include methods using a drill, a laser, and plasma.

[0113] Furthermore, when the composition layer is photosensitive, the method for forming a pattern having vias preferably includes a step of pattern-exposing the composition layer, a step of developing the exposed composition layer with a developer to form a pattern, and a step of etching the conductive layer in areas where the pattern is not arranged. It is more preferable to include a step of curing the pattern between the step of forming the pattern and the step of etching. The exposure may be performed from the side opposite the substrate of the composition layer, or from the substrate side of the composition layer.

[0114] Examples of the developer include an alkaline developer and an organic solvent developer. Examples of the development method include puddle development, shower development, spin development, and dip development, and a development method in which the developer is sprayed onto the composition layer after exposure by showering is preferred. After development, development residues may be removed by spraying a detergent or the like by showering and rubbing with a brush or the like. The temperature of the developer is preferably 20 to 40°C.

[0115] The light source used for exposure may be any light source that irradiates light in a wavelength range (e.g., light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.) to which various photosensitive components in the composition layer (e.g., polymerizable compounds, polymerization initiators, etc.) are sensitive. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

[0116] The exposure dose is 5 to 200 mJ / cm ２ is preferred, and 10 to 200 mJ / cm ２ is more preferred.

[0117] In step 2, exposure may be performed after peeling off the temporary support, or exposure may be performed through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off. It is preferable to perform patternwise exposure without peeling off the temporary support in order to prevent mask contamination due to contact between the composition layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure. The patternwise exposure may be exposure through a mask or direct exposure using a laser or the like. Examples of masks include quartz masks, soda-lime glass masks, and film masks. Quartz masks are preferred because of their excellent dimensional accuracy, and film masks are preferred because they can be easily made into large sizes. As a material for the film mask, polyester film is preferred, and polyethylene terephthalate film is more preferred. As a material for the film mask, for example, XPR-7S SG (manufactured by Fujifilm Global Graphic Systems Co., Ltd.) is exemplified.

[0118] The pattern having vias may be either through holes or via holes. The shape of the vias in the pattern may be, for example, a square, trapezoid, or inverted trapezoid in cross section; or a circle or square in front view (the shape of the via when observed from the direction in which the via bottom is visible). An inverted trapezoid is preferred as the cross section because it improves the adhesion of plated copper to the via wall surface. The via size (diameter) is preferably 300 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 5 μm or less. The lower limit is preferably 1 μm or more. The number of vias may be 1 or 2 or more, and preferably 2 or more.

[0119] <Step Z3> Step Z3 is a step of heating or exposing the composition layer. Step Z3 is preferably a step of curing the composition layer. The heating method is preferably the heating method in step X described above. The exposure method can be, for example, the exposure method in step Z2.

[0120] <Step Z4> Step Z4 is a step of forming a circuit pattern on the pattern. A semi-additive process is preferred as a method for forming a circuit pattern because it allows for the formation of fine wiring. For example, in the semi-additive process, a seed layer is first formed by electroless copper plating using a palladium catalyst or the like on the via bottoms, via walls, and the entire surface of a via-containing pattern. The seed layer is used to form a power supply layer for electrolytic copper plating, and the seed layer thickness is preferably 0.1 to 2.0 μm. A seed layer thickness of 0.1 μm or more tends to suppress a decrease in connection reliability during electrolytic copper plating. A seed layer thickness of 2.0 μm or less tends to eliminate the need for a large etching amount when flash etching the seed layer between wirings, thereby suppressing damage to the wiring during etching. Electroless copper plating is performed by reacting copper ions with a reducing agent to deposit metallic copper on the surface of the via-containing pattern. Examples of electroless plating methods and electrolytic plating methods include known plating methods. The catalyst for the electroless plating treatment is preferably a palladium-tin mixed catalyst. The average primary particle size of the mixed catalyst is preferably 10 nm or less. The plating solution for the electroless plating treatment preferably contains hypophosphorous acid (reducing agent). Examples of electroless copper plating solutions include "MSK-DK" manufactured by Atotech Japan and the "Sulcup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0121] The method for manufacturing a laminate may include a roughening step of roughening a pattern having vias. The roughening step is preferably performed after step Z3 and before step Z4. By performing the roughening step, the pattern surface can be roughened to improve adhesion with the circuit wiring. Smears can also be removed at the same time. Examples of the roughening step include known desmearing treatments, and treatments involving contact with a roughening liquid are preferred. Examples of the roughening liquid include a roughening liquid containing chromium and sulfuric acid, a roughening liquid containing an alkaline permanganate (e.g., a sodium permanganate roughening liquid, etc.), and a roughening liquid containing sodium fluoride, chromium, and sulfuric acid.

[0122] From the viewpoint of improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper, it is preferable to carry out a heat treatment after forming the circuit pattern. The heating temperature is preferably 150 to 240°C, and the heating time is preferably 15 to 500 minutes.

[0123] <Step Z5> Step Z5 is a step of forming a composition layer using a transfer film on the semiconductor package manufactured by the above-mentioned step Z4. The method of forming the composition layer using a transfer film is the same as the method in the above-mentioned step Z1, and the preferred embodiments are also the same.

[0124] Steps Z1 to Z5 may be repeated depending on the number of layers required. In addition, it is preferable to form a solder resist on the outermost layer of the resulting semiconductor package.

[0125] <Other Steps> The method for manufacturing a semiconductor package may include other steps in addition to the steps described above. Examples of such other steps include a step of peeling off the cover film, a step of reducing the visible light reflectance, and a step of performing an etching treatment. Examples of methods for peeling off the cover film include known methods. Suitable examples of treatments for reducing the visible light reflectance include those described in paragraphs

[0017] to

[0025] of JP 2014-150118 A and paragraphs

[0041] ,

[0042] ,

[0048] , and

[0058] of JP 2013-206315 A, the contents of which are incorporated herein by reference. Examples of etching methods include the wet etching method described in paragraphs

[0048] to

[0054] of JP 2010-152155 A, and known dry etching methods such as plasma etching.

[0126] A preferred method for manufacturing a laminate is to use a substrate having a plurality of conductive layers on both surfaces thereof, and to sequentially or simultaneously form patterns on the conductive layers formed on both surfaces. With the above configuration, a first conductive pattern can be formed on one surface of the substrate, and a second conductive pattern can be formed on the other surface. Formation from both surfaces of the substrate by roll-to-roll is also preferred.

[0127] [Semiconductor Package] The semiconductor package is not particularly limited as long as it includes the film of the present invention. The film may be used as an insulating film or as an organic interposer in a build-up base material.

[0128] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0129] [Preparation of Compositions] Methyl isobutyl ketone solutions (compositions) containing 40% by mass of each organopolysiloxane shown in the table below were prepared using solutions containing each organopolysiloxane obtained by the synthesis methods shown below. Other components shown in the table below were also added as necessary.

[0130] <Synthesis of Organopolysiloxanes A to E> Various SQ monomers and methyl isobutyl ketone (75.0 g) were mixed in a 300 mL three-neck flask in amounts appropriate for the structure of the target organopolysiloxane, and the mixture was stirred while heated to an external temperature of 80°C. A 0.1% by mass aqueous potassium hydroxide solution (18.0 g) was added dropwise at a constant rate over 5 minutes, and the mixture was stirred and heated for 5 hours. During heating, the reaction was carried out while removing refluxed methanol from the system using a Dean-Stark apparatus. After stopping the stirring and cooling to room temperature (25°C) in a water bath, methyl isobutyl ketone (150 g) and 5% by mass saline (150 g) were added, and the organic phase was extracted. The organic phase was washed once with 5% by mass saline (150 g) and twice with pure water (150 g), dried over magnesium sulfate (45 g), and then concentrated under a reduced pressure of 35 mmHg at 50°C to obtain a methyl isobutyl ketone solution containing any one of organopolysiloxanes A to E. As described above, each of the obtained methyl isobutyl ketone solutions containing organopolysiloxanes A to E was used to prepare each of the compositions.

[0131] <Synthesis of Organopolysiloxanes X, Y, and Z> Organopolysiloxanes X, Y, and Z were synthesized with reference to the above-mentioned method for synthesizing organopolysiloxanes. As described above, each composition was prepared using a methyl isobutyl ketone solution containing 40 mass% of each of the obtained organopolysiloxanes.

[0132] The structures of the organopolysiloxanes are shown below.

[0133]

[0134]

[0135] The structures of the monomers used in the synthesis of each organopolysiloxane and the synthesis routes are shown below.

[0136]

[0137] DMAc: dimethylacetamide THF: tetrahydrofuran TsCl: p-toluenesulfonyl chloride NMI: 1-methylimidazole

[0138]

[0139] EDCl: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride DMAP: 4-dimethylaminopyridine

[0140]

[0141] BuOAc: butyl acetate

[0142] Monomer SQ-E was synthesized with reference to the synthesis methods for each of the above-mentioned monomers.

[0143]

[0144]

[0145] Each composition was applied to an electrolytic copper foil (CF-T9DA-SV-18, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) as a substrate and dried at 100° C. to form a composition layer. The resulting composition layer was then heat-treated in an oven at the temperature and for the time shown in the table below, and then immersed in a 40% by mass aqueous solution of iron (III) chloride for 1 hour for a peeling treatment, followed by rinsing with pure water to obtain a film (cured film).

[0146] [Evaluation] <Proportion of the structure represented by formula (3)> The prepared film was crushed in a mortar and packed into a sample tube for solid-state NMR measurement to obtain a measurement sample. Then, using an NMR measurement device (manufactured by Bruker, Bruker AVANCE III 400WB / HX CP / MAS probe BL4, resonance frequency 400 MHz), measurement was performed under the following conditions: ２９ A Si CP / MAS NMR spectrum was obtained. The obtained spectrum was subjected to peak separation to obtain the area value of the peak derived from the structure represented by any one of formulas (3) to (6). Next, the ratio of the peak area derived from the structure represented by formula (3) to the sum of the peak areas derived from the structure represented by formula (3) in the film (100 × peak area derived from the structure represented by formula (3) / sum of peak areas derived from the structure represented by formula (3) to (6)) was calculated. The structure represented by any one of formulas (3) to (6) is as described above.

[0147] (Measurement conditions) Measurement method: CP / MAS １ H90° pulse width: 5 μs CP contact time: 2 ms Spectral width: 300 ppm Number of measurement data points: 2048 points MAS rotation speed: 5200 Hz (however, when multiple peaks were observed, the rotation speed was set so that the spinning side bands did not overlap with the main peak.)

[0148] (Evaluation Criteria) "A": The ratio of the structure represented by formula (3) is 85% or more. "B": The ratio of the structure represented by formula (3) is 75% or more but less than 85%. "C": The ratio of the structure represented by formula (3) is less than 75%.

[0149] <T ２ｃThe prepared film was ground in a mortar and packed into a solid-state NMR sample tube to prepare a measurement sample. Using an NMR measurement device (manufactured by Bruker, Bruker AVANCE III HD 400WB / HX CP / MAS probe BL4, resonance frequency 400 MHz), pulses were repeated L times at echo time intervals of 2τ by the CPMG method under the following conditions using a pulse program built into Bruker's control and measurement software "TopSpin 3.5," and the FID (free induction decay) signal after the echo time 2τ × L was measured, i.e., a total of 16 FID signals were measured. Furthermore, the FID signals were Fourier transformed to obtain １ The integrated area value of the region of -10 to 20 ppm of the H MAS NMR spectrum was obtained, and this value was used as the signal intensity (measured value). The signal intensity was plotted against each echo time (2τ × L) to obtain profile data. Next, the profile data was subjected to fitting processing using the above-mentioned formula (I) to obtain the relaxation time T ２ｃ Specifically, using the Solver add-in of Excel (registered trademark, manufactured by Microsoft Corporation), fitting was performed so as to minimize the sum of squares of the difference between the measured value of the signal intensity and the calculated value of the signal intensity calculated from formula (I), i.e., using the least squares method, and the waveform was separated into decay curves derived from components A, B, and C in order of shortest relaxation time, and the relaxation time T ２ｃ The decay curves derived from components A, B, and C were fitted as exponential functions.

[0150] (Measurement conditions) Pulse program: cpmg 90° pulse width: 2.6 μs 180° pulse width: 5.2 μs Echo pulse time interval τ: 40 μs Number of echo pulse irradiations: 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 30, 40, 60, 80, 100, 120 Number of accumulations: 8 times MAS rotation speed: 12 kHz Measurement temperature: room temperature (23° C.)

[0151] (Evaluation criteria) "A": T ２ｃ is 1.0 milliseconds or less "B": T ２ｃ is more than 1.0 milliseconds and 1.5 milliseconds or less "C": T ２ｃis more than 1.5 milliseconds and less than 2.0 milliseconds "D": T ２ｃ is more than 2.0 milliseconds and less than 3.0 milliseconds "E": T ２ｃ But it exceeds 3.0 milliseconds

[0152] <Glass Transition Temperature (Tg)> A portion of the film obtained above was cut out and used as a measurement sample. The glass transition temperature (Tg) of the obtained measurement sample was measured using a DSC (differential scanning calorimetry, "X-DSC7000" manufactured by Hitachi High-Tech Science Corporation). The measurement conditions were as follows: the temperature was increased from room temperature (25°C) to 250°C twice at a temperature increase rate of 10°C / min, and Tg was calculated from the peak change during the second temperature increase.

[0153] (Evaluation criteria) "A": Glass transition temperature is 100°C or higher "B": Glass transition temperature is 80°C or higher but lower than 100°C "C": Glass transition temperature is 70°C or higher but lower than 80°C "D": Glass transition temperature is 60°C or higher but lower than 70°C "E": Glass transition temperature is lower than 60°C

[0154] <Coefficient of Linear Expansion (CTE)> The prepared film was cut into strips (35 mm x 5 mm) to prepare measurement samples, and the coefficient of linear expansion was measured using a TMA (thermomechanical analyzer, "TMA450EM" manufactured by TA Instruments). The measurement conditions were a temperature rise rate of 10°C / min, a chuck distance of 20 mm, and a load of 45 mN. The coefficient of linear expansion was measured as a value (ppm / K) in the range of 30 to 50°C during temperature rise, and was calculated as the average value of three measurements. In practical use, a value of C or higher is preferable.

[0155] (Evaluation criteria) "A": Linear expansion coefficient is 70 ppm / K or less "B": Linear expansion coefficient is more than 70 ppm / K and less than 90 ppm / K "C": Linear expansion coefficient is more than 90 ppm / K and less than 110 ppm / K "D": Linear expansion coefficient is more than 110 ppm / K and less than 130 ppm / K "E": Linear expansion coefficient is more than 130 ppm / K

[0156] In the table, the "Number of Ring Structures" column indicates the total number of monocyclic ring structures among the rings contained in the units constituting the organopolysiloxane. The "Heteroatom of Ring Structure" column indicates "A" when the units constituting the organopolysiloxane have a mesogenic group, the group containing the mesogenic group contains one or more rings, and the monocyclic ring structure in the one or more rings contains a heteroatom, and "B" otherwise. The "Mw" column indicates the weight-average molecular weight of each organopolysiloxane measured by the method described above. The "Content (mass%)" column for each "Organopolysiloxane" indicates the content (mass%) of each organopolysiloxane relative to the total solids content of the composition. The "Crosslinker Content (mass%)" column indicates the content (mass%) of the crosslinker relative to the total solids content of the composition. The "Catalyst Content (mass%)" column indicates the content (mass%) of the catalyst relative to the total solids content of the composition. The "Heat Treatment" column indicates the conditions for the heat treatment in the above-mentioned film manufacturing method. The column "Proportion of structure represented by formula (3)" indicates the proportion of the structure represented by formula (3) measured by the above-mentioned method.

[0157]

[0158] Crosslinking agent

[0159]

[0160] catalyst

[0161]

[0162] From the evaluation results in the table, it was confirmed that the films of the present invention have a low linear expansion coefficient (Examples 1 to 17).

[0163] From a comparison between Examples 1, 2 and 4 and Examples 3 and 5 to 14, T ２ｃIt was confirmed that when the time t is 1.0 milliseconds or less, at least one of the glass transition temperature and the linear expansion coefficient is superior. From comparisons of Examples 1 and 2 with Example 3 (comparisons of Examples 4 and 5 with Example 6, comparisons of Examples 9 and 10 with Example 11, and comparisons of Examples 12 and 13 with Example 14), it was confirmed that when the ratio of the peak area derived from the structure represented by Formula (3) to the total peak areas derived from the structures represented by Formulas (3) to (6) is 75% or more, at least one of the glass transition temperature and the linear expansion coefficient is superior. From comparisons of Example 2 with Examples 5, 8, 10, and 12, it was confirmed that when the units constituting the organopolysiloxane have a mesogenic group, the group having the mesogenic group contains one or more rings, and the monocyclic ring structure in the one or more rings contains a heteroatom, both the glass transition temperature and the linear expansion coefficient are superior. Comparisons between Examples 1, 15, and 16 and Example 17 confirmed that the glass transition temperature was superior when the content of the organopolysiloxane containing the unit represented by formula (1) was 50% by mass or more relative to the total mass of the film (total solid content of the composition). Furthermore, comparisons between Examples 1 and 15 and Examples 16 and 17 confirmed that the linear expansion coefficient was superior when the content of the organopolysiloxane containing the unit represented by formula (1) was 80% by mass or more relative to the total mass of the film (total solid content of the composition).

[0164] [Semiconductor Package] The composition prepared in each example was applied to a temporary support (QS62, manufactured by Toray Industries, Inc., 31 μm thick PET film) and dried at 100°C to form a composition layer. A cover film (FG-201, polypropylene film, manufactured by Oji F-Tex Co., Ltd., 30 μm thick) was then attached to the side of the composition layer opposite the temporary support to obtain a transfer film. The resulting transfer film was laminated to both sides of a glass epoxy substrate (CCL-EL190T, 1.0 mm thick, manufactured by Mitsubishi Gas Chemical Co., Inc.) on which a circuit pattern had been formed, thereby forming composition layers on both sides of the glass epoxy substrate. Lamination was performed using a vacuum laminator manufactured by MCK Corporation under conditions of a substrate temperature of 50°C, a rubber roller temperature of 100°C, a linear pressure of 3 N / cm, and a conveying speed of 2 m / min. A pattern having vias with a diameter of 80 μm was formed at predetermined positions on the composition layer and subjected to a heat treatment (200°C, 1.5 hours). Residues were then removed using a sodium permanganate aqueous solution as a roughening solution, followed by electroless plating. Next, a resist pattern was formed at predetermined positions using a known dry film resist, followed by electrolytic plating, and the resist pattern was stripped using a stripping solution. Finally, a seed layer etching process was performed, followed by a heat treatment (180°C, 1 hour) to form copper wiring on the insulating film formed by the composition. The above process from lamination to heat treatment was repeated three times. Finally, a solder resist was formed as the outermost layer, and a semiconductor element was sealed and mounted to produce a semiconductor package. The resulting semiconductor package was mounted at a predetermined position on a printed wiring board to obtain a semiconductor package substrate. It was confirmed that the resulting semiconductor package substrate operated normally.

Claims

1. A film containing organopolysiloxane, wherein the signal intensity of the free induction decay of the spin-spin relaxation of all protons at room temperature is measured by the CPMG method of solid-state NMR for the film, and the signal intensity is subjected to fitting processing using formula (I), and the relaxation time T of component C is determined from three components, component A, component B, and component C, in order of shortest relaxation time. ２ｃ is less than 2.0 milliseconds. I=A×exp(-t / T ２ａ )+B×exp(-t / T ２ｂ )+C×exp(-t / T ２ｃ ) (I) A: component ratio of component A T ２ａ : Relaxation time of component A B: Component ratio of component B T ２ｂ : Relaxation time of component B C: Component ratio of component C T ２ｃ : relaxation time of component C t: echo time 2. T ２ｃ 10. The membrane of claim 1, wherein the time t is 1.0 milliseconds or less.

3. The film of claim 1, wherein the organopolysiloxane comprises a unit represented by formula (1): Formula (1) R ａ -SiO ３／２ R ａ represents a group having a mesogenic group.

4. The film according to claim 1, wherein, when the peak area derived from the structure represented by any one of formulas (3) to (6) is measured by Si-NMR measurement of the film, the ratio of the peak area derived from the structure represented by formula (3) to the total peak area derived from the structure represented by any one of formulas (3) to (6) is 75% or more. Formula (3) R-SiO ３／２ Formula (4) R-Si(OH)O ２／２ Formula (5) R-Si(OH) ２ O １／２ Formula (6) R-Si(OH) ３ Each R independently represents a monovalent substituent.

5. The film according to claim 3, wherein the group having a mesogenic group contains one or more rings, and the total number of monocyclic ring structures in the one or more rings is two or more.

6. The film according to claim 3, wherein the group having a mesogenic group has a heteroatom.

7. The film according to claim 3, wherein the group having a mesogenic group contains one or more rings, and a single ring structure in the one or more rings contains a heteroatom.

8. The film according to claim 3, wherein the content of the organopolysiloxane containing the unit represented by formula (1) is 50 mass % or more based on the total mass of the film.

9. The film according to claim 3, wherein the content of the organopolysiloxane containing the unit represented by formula (1) is 80 mass % or more based on the total mass of the film.

10. A semiconductor package comprising the film of any one of claims 1 to 9.

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