JP2003035668A - Quantitative determination method for protective rate of hydroxyl group in polymer compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method in which the protective rate of a hydroxyl group can be quantitatively determined in a short time and with satisfactory accuracy without isolating a polymer compound composed of a first structure unit and a second structure unit shown below from a measuring sample: The first structure unit is a structure unit as a structure having a hydroxyl group, e.g. a structure unit (I), and the second structure unit is a structure unit as a structure in which a protecting group is introduced into the hydroxyl group in the first structure unit, e.g. a structure unit (II). SOLUTION: Near-infrared absorption spectra of a plurality of standard samples are principal-regression-analyzed, and a multiple-regression working curve is obtained. By using the multiple-regression working curve, the protective rate of the polymer compound contained in the sample is calculated on the basis of the near-infrared absorption spectrum of the measuring sample. When the polymer compound is manufactured by reacting a protective agent with a raw-material polymer compound or by desorbing the protecting group from the raw-material polymer compound, the protective rate of the polymer compound contained in a reaction mixture in the halfway part of a reaction is measured, and the reaction is stopped on the basis of the protective rate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for quantifying the protection rate of hydroxyl groups of a polymer compound.

[0002]

2. Description of the Related Art The following polymer compound consisting of a first structural unit and a second structural unit is useful, for example, as a resin component of a photoresist. First structural unit: structural unit having a structure having a hydroxyl group Second structural unit: structural unit having a structure in which a protective group is introduced into the hydroxyl group in the first structural unit

In such a polymer compound, the protection rate of hydroxyl groups, which is the content ratio of the first structural unit and the second structural unit, is important. An NMR method for quantifying from the nuclear magnetic resonance (NMR) spectrum of a compound is known (Japanese Patent Laid-Open No. H5-
249682, JP-A-8-123032,
JP-A-10-147614).

However, the NMR method has a problem that it takes a relatively long time to measure an NMR spectrum. Further, when the polymer compound is included in the measurement sample together with the impurities, it was necessary to measure the NMR spectrum after pretreatment for isolating the polymer compound from the measurement sample.

As a quantitative method capable of quantifying the protection rate of the hydroxyl groups of the polymer compound in a short time without isolating the polymer compound from the measurement sample, the measurement sample is thermally decomposed and the produced fragment is quantified by gas chromatography. Pyrolysis gas chromatographic method is used, but such a method is not a highly accurate quantification method because it is a method of thermally decomposing and quantifying a polymer compound.

[0006]

Therefore, the present inventors have found that
As a result of diligent studies to develop a quantitative method that can accurately quantify the protection rate of the hydroxyl group of a polymer compound in a short time without isolating the polymer compound from the measurement sample, the near infrared absorption spectra of multiple standard samples Using a multiple regression calibration curve obtained by principal component analysis, by calculating the protection rate from the near-infrared absorption spectrum of the measurement sample containing a polymer compound, even when the measurement sample contains impurities, The inventors have found that the protection rate of the hydroxyl groups of the polymer compound contained in the measurement sample can be quantified accurately in a short time, and have reached the present invention.

[0007]

Means for Solving the Problems That is, the present invention is based on the near-infrared absorption spectra of a measurement sample containing a polymer compound consisting of the following first structural unit and second structural unit. A multiple regression calibration curve obtained by subjecting an absorption spectrum to principal component regression analysis is used to calculate a hydroxyl group protection rate of the polymer compound. It is a thing. First structural unit: structural unit having a structure having a hydroxyl group Second structural unit: structural unit having a structure in which a protective group is introduced into the hydroxyl group in the first structural unit

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A measurement sample applied to the quantification method of the present invention contains a polymer compound composed of the first structural unit and the second structural unit. The first structural unit is a structural unit having a structure having a hydroxyl group, and examples of such a structural unit include those represented by the formula (I) And a structural unit having a phenolic hydroxyl group such as the structural unit represented by.

The second structural unit is a structural unit having a structure in which a protective group is introduced into the hydroxyl group in the first structural unit.
Examples of the protective group include an alkoxyalkyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyl group,
Examples thereof include an alkoxycarbonyl group. The alkoxyalkyl group includes, for example, an ethoxyethyl group, a cyclohexyloxyethyl group, an ethoxypropyl group, the alkylcarbonyl group includes, for example, a pivaloyl group, and the arylcarbonyl group includes, for example, a benzoyl group, and an alkyl group. Examples thereof include a methyl group, an ethyl group and an isopropyl group, and examples of the alkoxycarbonyl group include a t-butyloxycarbonyl group. The number of such protecting groups may be one, or two or more.

When the first structural unit is the structural unit represented by the above formula (I), the second structural unit is represented by the formula (II) (In the formula, Z represents a protecting group.).

The polymer compound consisting of the first structural unit and the second structural unit may contain other structural units. Examples of other structural units include acrylic acid units, methacrylic acid units, t-butyl acrylate units, t-butyl methacrylate units, cyclohexyl acrylate units, cyclohexyl methacrylate units, adamantyl acrylate units, adamantyl methacrylate units, 2-Hydroxyadamantyl acrylate unit, 2-hydroxyadamantyl methacrylate unit, 2-methyladamantyl acrylate unit, 2-methyladamantyl methacrylate unit, 2-ethyladamantyl acrylate unit, 2-ethyladamantyl methacrylate unit, acrylic acid 1
Examples include-(1'-adamantyl) methylethyl unit, 1- (1'-adamantyl) methylethyl methacrylate unit, and styrene unit.

Such a polymer compound can be produced, for example, by a method of reacting a starting polymer compound comprising the first structural unit with a protective agent (Japanese Patent Laid-Open No. 5-249).
682, JP-A-8-123032, JP-A-10-147614). According to such a method, a protecting group is introduced into the hydroxyl group of the raw material polymer compound by the protecting agent, the first structural unit is converted into the second structural unit, and the first structural unit and the second structural unit. It is possible to obtain a polymer compound consisting of

It can also be produced by a method in which the protective group is eliminated from the starting polymer compound composed of the second structural unit (JP-A-5-249682 and JP-A-8).
-1223032, JP-A-10-147614, etc.). According to such a method, the protective group of the starting polymer compound is eliminated, the second structural unit is converted into the first structural unit, and the polymer compound composed of the first structural unit and the second structural unit Can be obtained.

The quantification method of the present invention is a method for quantifying the degree of protection of hydroxyl groups of a polymer compound composed of such a first structural unit and a second structural unit.

The quantification method of the present invention will be described below by taking the case of quantifying the protection rate of the hydroxyl groups of the polymer compound contained in the reaction mixture during the reaction in the above production method as an example.

The measurement sample used in the quantification method of the present invention may be a reaction mixture during the reaction or a reaction mixture after completion of the reaction. The measurement sample containing such a high molecular compound can be collected by a usual method, for example, a method using a pipette, a microsyringe or the like from the reaction mixture during the reaction or the reaction mixture after the reaction is completed. The measurement sample after measuring the near-infrared absorption spectrum may be returned to the reaction mixture. Further, the measurement sample may be continuously taken from the reaction mixture, and in this case, the measurement sample after measurement is usually continuously returned to the reaction mixture.

In the quantification method of the present invention, the polymer compound may be isolated from the reaction mixture thus collected during or after the reaction, and the obtained polymer compound may be used as a measurement sample.

The near-infrared absorption spectrum (x) of the measurement sample is measured by using a normal infrared spectroscopic analyzer such as a Fourier transform infrared spectroscopic analyzer (FT-IR device) or a wavelength dispersion infrared spectroscopic analyzer. be able to. The measurement wave number range is usually 12,500 to 4000 cm ^-1
It is selected from a range of degrees.

The obtained spectrum (x) is converted into the hydroxyl group protection rate (y) of the polymer compound using a multiple regression calibration curve. The multiple regression calibration curve is obtained by subjecting the near-infrared absorption spectra of a plurality of standard samples to a principal component regression analysis. Specifically, for example, a computer is used to perform the main component according to the following [Procedure 1] to [Procedure 7]. It can be obtained by performing regression analysis.

[Procedure 1] From the protection rate (n _i1 ) of hydroxyl groups of polymer compounds contained in N standard samples, the formula (1-
1) The procedure for obtaining the matrix [N] according to

[Procedure 2] A procedure for preparing a matrix [R] in which the near infrared absorption spectra (r _i ) of N standard samples are used as column vectors and r _i are arranged in columns.

[Procedure 3] Matrix [R] and its transposed matrix
Autocorrelation matrix of [R] obtained from the ^t [R] [R] [R] ^t the eigenvectors (u _j) is a matrix arranged in columns [U], the matrix [R] autocorrelation matrix of ^t [R] ^t The matrix [V] in which the eigenvectors (v _m ) of [R] are arranged in columns and the diagonal matrix [Λ] having the eigenvalues (λ _p ) of the autocorrelation matrix [R] [R] ^t as diagonal elements are obtained. procedure.

[Procedure 4] Inverse matrix [Λ] of [N], [V], and [Λ]
⁻¹ , the inverse matrix [U] ^{−1 of} [U] and [R] are used to calculate the equation (4-1) [N ′] = [N] [V] [Λ] ⁻¹ [U] ⁻¹ [R] ( A procedure for obtaining the matrix [N ′] according to 4-1).

[Procedure 5] From the element n _i1 of [N] and the element n ′ _i1 of [N ′] for all i, equation (5-1) The procedure for obtaining the error (e) calculated by

[Procedure 6] The error (e) is calculated by changing the wave number range of the spectrum (r _i ) used in the above procedure 2 and the pretreatment applied to the spectrum (r _i ) and performing the calculations of the above procedure 2 to procedure 5. determined, the procedure for selecting the processing prior to applying the error wavenumber range and spectrum of the spectrum to be used for calculation as (e) is minimized _{(r i) (r i)} .

[Procedure 7] [V], [Λ] ⁻¹ and [U] ⁻ calculated by subjecting the spectrum (r _i ) in the wave number range selected in Procedure 6 to the preprocessing selected in Procedure 6 above. ^{1 and} [N]
The procedure of obtaining the matrix [T] indicating the multiple regression calibration curve by the equation (7-1) [T] = [N] [V] [Λ] ^-1 [U] ^-1 (7-1) using .

FIG. 1 shows the relationship between the above [Procedure 1] to [Procedure 7].
Shown in. Hereinafter, [Procedure 1] to [Procedure 7] will be described in detail.

[Procedure 1] From the protection rate (n _i1 ) of hydroxyl groups of polymer compounds contained in N standard samples, the formula (1-
A procedure for obtaining the matrix [N] according to 1). The protection rate of the hydroxyl group of the polymer compound contained in the standard sample is known.
In the matrix [N] shown in Expression (1-1), N is the number of standard samples, and i is a natural number of 1 to N. M is the rank (rank) of the self-dispersion matrix [R] [R] ^t obtained from the transposed matrix [R] ^{t of} [R] and [R] described later, that is, the number of non-zero eigenvalues. The eigenvalue, which is a value less than the variance of the noise of the spectrum (r _i ) may be regarded as 0.
Of the elements of the matrix [N], n _i1 is the protection rate (y) of the hydroxyl groups of the polymer compound contained in each standard sample. For example, the number of hydroxyl groups (N ₁ ) of the first structural unit of the polymer compound and It is a value defined by the formula (1) y = N ₂ / (N ₁ + N ₂ ) (1) from the number (N ₂ ) of protecting groups of the second structural unit. The protection rate (y) can be accurately quantified by, for example, an NMR method. Other elements n _ik of the matrix [N] (k is a natural number of 2 to M.) Are mutually independent variables for each standard sample, for example, the reaction initial concentration of the raw material polymer compounds, the raw material polymer compounds Degree of polymerization, if the starting polymer compound contains another structural unit, its content, the concentration of the protective agent used,
The concentration of by-products, and when the solvent used in the reaction is a mixed solvent of a plurality of solvents, its composition ratio and the like can be mentioned. If the number of variables of each standard sample is less than M, it is sufficient to calculate the same value that is not 0 for all _ni k that is less than that, for example, 1 but the error (e) obtained in step 5
Tends to deviate from zero. Note that M is smaller than N, and when M matches N, N, that is, the number of standard samples may be increased.

[Procedure 2] A procedure for preparing a matrix [R] in which the near infrared absorption spectra (r _i ) of N standard samples are used as column vectors and r _i are arranged in columns. The near-infrared absorption spectrum (r _i ) of N standard samples is represented by the formula (2-1) where the absorbance at the h-th wave number is r _ih Is a column vector, and H is the number of measured wave numbers. The matrix [R] is the equation (2-2) It becomes the matrix shown by. For all i, the spectrum (r _i ) may be the measured spectrum as it is, the wave number range may be limited in advance, or pre-processing, for example, baseline correction processing such as processing for subtracting the average value, Background processing, smoothing processing, 1
Processing such as differential processing such as secondary differential, secondary differential, and tertiary differential may be performed. These pretreatments are performed individually or in combination of two or more treatments.

[Procedure 3] Matrix [R] and its transposed matrix
Autocorrelation matrix of [R] obtained from the ^t [R] [R] [R] ^t the eigenvectors (u _j) is a matrix arranged in columns [U], the matrix [R] autocorrelation matrix of ^t [R] ^t The matrix [V] in which the eigenvectors (v _m ) of [R] are arranged in columns and the diagonal matrix [Λ] having the eigenvalues (λ _p ) of the autocorrelation matrix [R] [R] ^t as diagonal elements are obtained. procedure. The eigenvectors (u _j ) and (v _m ) and the eigenvalue (λ _p ) can be obtained by ordinary methods such as numerical calculation using a computer. j, m,
p is a natural number of 1 to M, respectively.

[U] is the equation (3-1). And the matrix [V] is given by equation (3-2) And the matrix [Λ] is given by equation (3-3). It becomes the matrix shown by.

However, normally, λ _p satisfies the equation (3-4) λ ₁ > λ ₂ > ... λ _M > 0 (3-4), and the eigenvector (u _j ) is an equation ( 3-
5) | u _j | = 1 (3-5) is satisfied, and the eigenvector (v _m ) is expressed by the formula (3-
6) Normalized and calculated so as to satisfy | v _m | = 1 (3-6).

The matrix [U] satisfies the equation (3-7) [R] [R] ^t = [U] [Λ] [Λ] [U] ^t (3-7), and the matrix [V] is Expression (3-8) [R] ^t [R] = [V] [Λ] [Λ] [V] ^t (3-8) is satisfied.

[Procedure 4] Inverse matrix [Λ] of [N], [V], and [Λ]
^-1 , a procedure of obtaining the matrix [N '] from the inverse matrices [U] ^-1 and [R] of [U] according to the equation (4-1). Inverse matrix [Λ] ^-1 and
[U] ^-1 can be obtained from [Λ] and [U] by a usual method such as a numerical calculation method using a computer.

[Procedure 5] A procedure for obtaining the error (e) calculated by the equation (5-1) from the element n _i1 of [N] and the element n ′ _i1 of [N ′] for all i. The element n _i1 of [N] is the measured value of the protection rate (y) of each standard sample, and the element n ′ _i1 of [N ′] is calculated from the spectrum (r _i ) and eigenvector (u _j ) of each standard sample. The calculated protection rate.
Under ideal conditions where there is no noise in the spectrum (r _i )
The element n _i1 of [N] and the element n ′ _i1 of [N ′] are mathematically identical and the error (e) is 0, but the actual spectrum (r _i ) contains noise. The measured value (n _i1 ) of the protection rate and the calculated value (n ′ _i1 ) of the protection rate obtained by the equation (4-1) do not mathematically match, and the error (e) is usually a value other than 0. ,
That is, the value becomes larger than 0.

[Procedure 6] The error (e) is calculated by changing the wave number range of the spectrum (r _i ) of the standard sample used in the above procedure 2 and the pretreatment, and the error (e) is calculated. ) Is the minimum, the wave number range of the spectrum (r _i ) of the standard sample used for the calculation, and the procedure for determining the pretreatment. The wave number range of the spectrum (r _i ) used for calculation is
If it is wide, the accuracy of calculation of the protection rate (n ′ _i1 ) can be improved, but the storage capacity of the computer required for the calculation of the multiple regression calibration curve becomes large and the calculation takes a long time. On the contrary, when the wave number range is narrowed, the accuracy of calculation of the protection rate (n ' _i1 ) becomes low. Therefore, the wave number range of the spectrum (r _i ) used for the calculation is appropriately selected in consideration of the storage capacity of the computer used, the calculation speed, the desired accuracy of the protection rate (y), and the like.

As the preprocessing of the spectrum (r _i ), the same processing as that described above in step 2, for example, baseline correction processing such as processing for subtracting the average value, background processing, smoothing processing, first derivative, second order Differentiation, 3
A process such as a differential process such as a next differential process may be used. These pretreatments are performed individually or in combination of two or more treatments.

[Procedure 7] The above-mentioned procedure 6 is added to the data (absorbance) in the wave number range selected in the above-mentioned procedure 6 of the spectrum (r _i ).
[V], [Λ] ⁻¹ and [U] ^{−1 and} [N] calculated by performing the pre-processing selected in step (7) are used to calculate a matrix showing a multiple regression calibration curve. Procedure for obtaining [T].

In the principal component regression analysis shown in the above [Procedure 1] to [Procedure 7], the protection rate (y) was calculated in [Procedure 1].
Was defined by the formula (1), but the protection rate (y) may be defined by the formula (2) y = N ₁ / (N ₁ + N ₂ ) (2) instead of the formula (1). It may also be defined as the ratio of the number of the second structural unit to the total number of the first structural unit, the second structural unit and the other structural unit,
It may be defined as the ratio of the number of first structural units to the total number.

Further, in [Procedure 5], the error (e) calculated by the equation (5-1) is obtained, and in [Procedure 6], the spectrum (r _i used for the calculation is made so that this error (e) is minimized. ), The wave number range and the preprocessing are determined, but instead of the error (e), the elements n _i1 of [N] for all i are
The correlation coefficient with the element n ′ _i1 of [N ′] is obtained, and in [Procedure 6], the wave number range of the spectrum (r _i ) used in the calculation and the preprocessing are performed so that the correlation coefficient is closest to 1. You may decide.

In the quantification method of the present invention, the multiple regression calibration curve (matrix [T]) thus obtained is used to calculate the protection rate (y) from the near infrared absorption spectrum (x) of the measurement sample.

The near-infrared absorption spectrum (x) of the measurement sample is expressed by the formula (3), where the absorbance at the h-th wave number is x _h. Is a column vector represented by. To obtain the protection rate (y) from the near-infrared absorption spectrum (x) of the measurement sample using the multiple regression calibration curve (matrix [T]), for example, the protection rate (y), the near-infrared absorption spectrum (x) and the weight The near-infrared absorption spectrum (x) may be substituted into the relational expression of the regression calibration curve (matrix [T]). Specifically, the near-infrared absorption spectrum (x) of the measurement sample and the matrix [ T] and equation (4) The protection rate (y) may be calculated as the _first element (w ₁ ) of the column vector (w) calculated by

Thus, the protection rate (y) obtained from the multiple regression calibration curve has the same accuracy as the protection rate quantified by the same quantification method as that used for quantifying the protection rate of the hydroxyl group of the polymer compound contained in the standard sample. In the case where the protection rate of the hydroxyl groups of the polymer compound contained in the standard sample is quantified by the quantification method by the NMR method as exemplified in the above description, it is consistent with the protection rate quantified by the NMR method. ing.

According to the quantification method of the present invention, even when the measurement sample contains contaminants, the polymer compound contained in the measurement sample can be quickly and accurately prepared without isolating the polymer compound from the measurement sample. Since it is possible to obtain the protection rate of the hydroxyl group of, for example, by reacting the starting polymer compound consisting of the first structural unit with a protective agent to give a polymer compound consisting of the first structural unit and the second structural unit In the production, from the near-infrared absorption spectrum (x) of the reaction mixture during the reaction, using the multiple regression calibration curve, to calculate the protection rate of the hydroxyl group of the polymer compound contained in the reaction mixture,
If the reaction is stopped based on the obtained protection rate, it is possible to easily obtain a polymer compound having a desired protection rate.

To stop the reaction based on the obtained protection rate, when the protection rate (y) is defined by the formula (1),
The reaction may be stopped when the protection rate (y) reaches a target value, and the reaction may be continued as it is when the protection rate (y) is smaller than the target value. Also,
When the protection rate (y) is defined by the formula (2), the reaction may be stopped when the protection rate (y) has a target value, and the protection rate (y) is the target. When it is larger than the value, the reaction may be continued.

To stop the reaction, for example, the reaction mixture may be cooled to a temperature lower than the reaction temperature, or a reaction terminator may be added. When the reaction is continued, the protecting agent may be added when it is consumed and disappears. The reaction between the raw material polymer compound and the protecting agent is usually carried out in a solvent, and can also be carried out in the presence of a catalyst. The starting polymer compound may contain a smaller amount of the second structural unit than the content of the second structural unit in the target polymer compound. When the starting polymer compound contains another structural unit, a polymer compound composed of the first structural unit, the second structural unit and the other structural unit can be obtained.

In addition, when the protecting group is eliminated from the starting polymer compound comprising the second structural unit to produce the polymer compound comprising the first structural unit and the second structural unit, the reaction during the reaction is carried out. From the near-infrared absorption spectrum (x) of the mixture, using the above multiple regression calibration curve, calculate the protection rate of the hydroxyl groups of the polymer compound contained in the reaction mixture, and stop the reaction based on the obtained protection rate. By doing so, it is possible to easily obtain a polymer compound having a desired protection rate.

In order to terminate the reaction based on the obtained protection rate, when the protection rate (y) is defined by the formula (1),
For example, the reaction may be stopped when the protection rate (y) reaches a target value, and the reaction may be continued as it is when the protection rate (y) is larger than the target value.
Further, when the protection rate (y) is defined by the equation (2),
The reaction may be stopped when the protection rate reaches a target value, and the reaction may be continued as it is when the protection rate (y) is smaller than the target value.

To stop the reaction, for example, the reaction mixture may be cooled or a reaction terminator may be added. The reaction for removing the protective group from the raw material polymer compound is usually carried out in a solvent, and can also be carried out in the presence of a catalyst. The starting polymer compound may contain a smaller amount of the first structural unit than the content of the first structural unit in the target polymer compound. When the starting polymer compound contains another structural unit, a polymer compound composed of the first structural unit, the second structural unit and the other structural unit can be obtained.

[0050]

According to the quantification method of the present invention, a polymer compound contained in a measurement sample can be obtained without isolating the polymer compound comprising the first structural unit and the second structural unit from the measurement sample. The protection rate of hydroxyl groups can be accurately quantified in a short time. Further, the polymer compound is produced by a method of reacting a starting polymer compound composed of a first structural unit with a protecting agent, or a method of removing a protecting group from a raw material polymer compound composed of a second structural unit. At this time, the protection rate of the polymer compound contained in the reaction mixture during the reaction can be quantified quickly and accurately, so that the reaction can be stopped based on the protection rate, and as a result, the protection rate is a target value. A molecular compound can be easily manufactured.

[0051]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The protection rate of the polymer compound in each example was defined according to the formula (1).

Example 1 [Preparation of Standard Sample] (Lot 1-1) 25 parts by mass of poly (p-vinylphenol) (raw polymer compound, weight average molecular weight: 15,000 (polymerization degree: 125), paratoluenesulfonic acid 0.002 parts by weight of monohydrate (catalyst) and 150 parts by weight of methyl isobutyl ketone (solvent) were mixed and stirred to obtain a mixture, and a part of the obtained mixture was sampled to prepare a standard sample 1-.
1 (1 part by mass).

While stirring the mixture obtained above, 5.1 parts by mass of ethyl vinyl ether (protecting agent) was added dropwise over 30 minutes. Then, with stirring at 25 ° C., the reaction mixture after 1 hour, 2 hours or 3 hours after completion of the dropping was taken out, and standard samples 1-2 to 1-4 were respectively taken out.
(1 part by mass).

(Lot 1-2 to Lot 1-6) Except for changing the scale, the same operation as described above was performed to obtain lot 1-2 to lot 1-6, and the standard sample 1-5 was prepared in the same manner as above.
~ 1-21 (1 part by mass) was obtained. Standard sample 1-1 ~
Tables 1 and 2 show the relationship between 1-21 and the lot and take-out time. In addition, in the table, 0 hour later indicates the time when the dropping is completed.

[Determination of Protection Rate of Standard Sample by NMR Method] Triethylamine (0.1 part by mass) was added to the obtained standard sample (1 part by mass) and stirred, and n-heptane (5 parts by mass) was added. A polymer compound was deposited by using the above method. The precipitated polymer compound (powder) is collected by filtration, dried and
¹ H-NMR spectrum was measured. ^{From the 1} H-NMR spectrum, it was confirmed that a polymer compound in which a protecting group (ethoxyethyl group) was introduced into the hydroxyl group of poly (p-vinylphenol) was produced. ^{From the 1} H-NMR spectrum, the protection rate of the hydroxyl group of the polymer compound (n _i1 , i = 1)
.About.21) was calculated. The results are shown in Tables 1 and 2.

[Measurement of near-infrared absorption spectrum of standard sample] Near-infrared absorption spectrum of standard sample (r ₁
˜r ₂₁ ) is an FT-IR device [“Vector 22 /
N ", a wave number range 12000～5300Cm ^-1 by a transmission method using a Bruker] was determined by measuring with a resolution 2 cm ^-1, 8 cumulative. An example of a near infrared absorption spectrum is shown in FIG. 2 (standard sample 1-14), FIG. 3 (standard sample 1-15) and FIG. 4 (standard sample 1-19).

[Preparation of Multiple Regression Calibration Curve] The wave number range used for the calculation of the near infrared absorption spectrum (r _{1 to} r ₂₁ ) of the standard sample obtained above was set to 7500 to 5450 cm ⁻¹ (data point is 1026 points), Baseline correction was performed as pre-processing, and matrix [R] was calculated according to procedure 2 to procedure 3, matrix [U] was calculated, and rank (M) was calculated. M was 8.
Using the protection rate (n _i1 , i is 1 to 21) of the standard sample obtained from the above ¹ H-NMR spectrum, the above formula (1-
The matrix [N] was obtained based on 1). Note that _nik (i is 1 to 2
1 and k represent 2 to 8, respectively. ) Was set to 1. When [N ′] was obtained according to the procedure 4 and the error (e) was obtained according to the procedure 5, the value was 0.559. The protection rate (n _i1 , i = 1 to 21) at this time and the element (n ^′ _i1 ) of the matrix [N ′]
The relationship with is shown in FIG. Also, n ^′ _i1 is shown in Table 1 and Table 2.
Shown in.

[0058]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard Lot extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 1-1 1 1-1 Before dropping 0 0.41 1 1-2 1 1-1 1 hour later 36.9 37.67 2 1-3 3 1-2 2 hours later 37.6 36.85 3 1--4 1-1 3 hours later 37.5 37.14 4 ──────────── ───────────────────── 1-5 1-2 Before dropping 0-0.90 5 1-6 1-2 1-2 hours later 27.0 27.74 6 1-7 1 1- 2 2 hours later 27.0 27.53 7 1-8 8 1-2 3 hours later 26.9 27.14 8 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━

[0059]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 1-9 1-3 Before dropping 0 -0.90 9 1 -10 1-3 after 0 hours 26.1 25.29 10 1-11 1-3 after 1 hour 37.9 37.33 11 1-12 12-3 after 2 hours 38.2 38.39 12 1-13 1-3 after 3 hours 37.8 38.21 13 ──────────────────────────────── 1-14 1-4 Before dropping 0 0.85 14 1-15 15 1- 40 hours later 27.0 27.50 15 1-16 16-4 1 hour later 38.0 37.57 16 1-17 1-4 4 hours later 38.7 38.21 17 1-18 1-4 3.5 hours later 39.5 39.09 18 1-19 1-4 3 After 39.2 39.08 19 ────────────────────────── ───── 1-20 1-5 2.5 hours later 27.7 27.40 20 ───────────────────────────────── 1 -21 1-6 2.5 hours later 29.1 29.32 21 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

Then, according to procedure 7, a matrix [T] showing a multiple regression calibration curve was obtained. The spectrum (r
It was determined error (e) in the same manner as described above by changing the wave number range and pretreatment used to calculate the ₁ ~r _21), but none was greater than 0.559.

[Preparation of Measurement Sample] Poly (p-vinylphenol) (raw polymer compound, weight average molecular weight is 1)
5,000 (degree of polymerization: 125)) 25 parts by mass, paratoluenesulfonic acid monohydrate (catalyst) 0.002 parts by mass, and methyl isobutyl ketone (solvent) 150 parts by mass are mixed and stirred to obtain a mixture, which is measured. Sample 1-22 (1 part by mass) was collected. While stirring the mixture obtained above, 5.1 parts by mass of ethyl vinyl ether (protecting agent) was added dropwise over 30 minutes. Then, while stirring at 25 ℃,
At the completion of dropping (after 0 hour), the reaction mixture after 1 hour, 2 hours, and 3 hours after the completion of dropping was taken out as measurement samples 1-23 to 1-26 (1 part by mass), respectively.

[Determination of protection rate by NMR method] Measurement sample 1-22 in the same manner as in the standard sample
The ¹ H-NMR spectrum of 1-26 was measured to determine the protection rate. The results are shown in Table 3.

[Determination of Protection Rate Using Multiple Regression Calibration Curve] The near-infrared absorption spectrum (x) of the measurement samples 1-22 to 1-26 was determined in the same manner as in the standard sample, and out of the spectra (x) Number range 7500-5450
Using the data of cm ^-1 (the number of data points is 1026 points), a baseline correction was performed as a pretreatment to obtain a protection rate (y). The results are shown in Table 3. The time required for measuring the near infrared absorption spectrum was within 30 seconds. When the spectrum (x) was subjected to pretreatment to obtain the protection rate, an ordinary personal computer was used, and the protection rate could be obtained almost instantly.

[0064]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━ Measurement take-out time Protection rate (%) Protection rate (%) Sample NMR method y ━━━━━━━━━━━━━━━━━━━━━━━ 1-22 Before dropping 0-0.2 1-23 0 hours later 9.5 7.5 1-24 1 hour later 25.7 25.0 1-25 2 hours later 27.2 27.6 1-26 3 hours later 27.2 27.5 ━━━━━━━━━━━━━━━━━━━━━━━

As shown in Table 3, the calculated value of the protection rate calculated from the near infrared absorption spectrum (x) of the sample by using the multiple regression calibration curve agrees with the quantitative value of the protection rate obtained by the NMR method. There is.

Example 2 [Preparation of standard sample] (Lot 2-1) Copolymer of p-vinylphenol and cyclohexyl acrylate [raw polymer compound, weight average molecular weight 13000, p-vinylphenol monomer] The unit (first structural unit) is 90% in mole fraction, the cyclohexyl acrylate monomer unit (other structural unit) is 10% in mole fraction] 100 parts by mass, paratoluenesulfonic acid monohydrate ( A catalyst, 0.011 part by mass) and 600 parts by mass of methyl isobutyl ketone (solvent) were mixed and stirred to obtain a mixture.

While stirring the mixture obtained above, 23.4 parts by mass of ethyl vinyl ether (protecting agent) was added dropwise over 30 minutes. After that, while stirring at 25 ° C., at the completion of the dropping (after 0 hours), 1 hour after the completion of the dropping, and 2 hours after the completion of the dropping, the reaction mixture was sampled twice to obtain standard samples 2-1 to 2-6 (each). 1 part by mass).

Thereafter, the mixture was stirred at the same temperature for about 1 hour, ethyl vinyl ether (1.3 parts by mass) was further added with stirring at the same temperature, and with stirring at the same temperature, 1 hour after the addition (+1 hour later) It was sampled twice from the reaction mixture of the above) to obtain standard samples 2-7 to 2-8 (each 1 part by mass). Table 4 shows the take-out time of each standard sample.

(Lot 2-2) As a raw material polymer compound, a copolymer of p-vinylphenol and cyclohexyl acrylate [raw material polymer compound, weight average molecular weight is 1
3000, p-vinylphenol monomer unit (first structural unit) is 85% by mole fraction, cyclohexyl acrylate monomer unit (other structural units) is 15% by mole fraction] Then, standard samples 2-9 to 2-18 were obtained in the same manner as in lot 2-1 except that the amount of ethyl vinyl ether added was 20.1 parts by mass. Table 5 shows the take-out time of each standard sample.

(Lot 2-3) The same procedure as in Lot 2-2 was conducted except that the amount of ethyl vinyl ether added dropwise was 14.5 parts by mass and no additional ethyl vinyl ether was used. 19 to 2-26 were obtained. Table 6 shows the take-out time of each standard sample.

(Lot 2-4) Lot 2 was used except that the amount of ethyl vinyl ether added dropwise was 22.7 parts and no additional ethyl vinyl ether was used.
Operate in the same manner as for -1, and standard samples 2-27 to 2-3
Got 2. Table 7 shows the take-out time of each standard sample.

(Lot 2-5) Same as Lot 2-2 except that the amount of ethyl vinyl ether added dropwise was 22.6 parts by mass and the amount of additional ethyl vinyl ether was 0.9 parts by mass. The standard sample 2-
33 to 2-40 were obtained. Table 8 shows the take-out time of each standard sample.

(Lot 2-6) Standard sample 2 was prepared in the same manner as in lot 2-2 except that the amount of ethyl vinyl ether added dropwise was 16.3 parts by mass and no additional ethyl vinyl ether was used. -41 to 2-46 were obtained. Table 9 shows the take-out time of each standard sample.

(Lot 2-7) Same as Lot 2-2 except that the amount of ethyl vinyl ether added dropwise was 23.2 parts by mass and the amount of additional ethyl vinyl ether was 2.5 parts by mass. The standard sample 2-
47 to 2-56 were obtained. Table 10 shows the take-out time of each standard sample.

(Lot 2-8) Same as lot 2-1 except that the amount of ethyl vinyl ether added dropwise was 21.7 parts by mass and the amount of additional ethyl vinyl ether was 1.8 parts by mass. Operate the standard sample 2-5
7-2-62 was obtained. Table 1 shows the extraction time of each standard sample.
Shown in 1.

(Lot 2-9) Same as Lot 2-2 except that the amount of ethyl vinyl ether added dropwise was 20.2 parts by mass and the amount of additional ethyl vinyl ether was 2.4 parts by mass. The standard sample 2-
63 to 2-70 were obtained. Table 12 shows the take-out time of each standard sample.

(Lot 2-10) 100 parts by mass of the same raw material polymer compound as used in lot 2-1 were mixed with paratoluenesulfonic acid monohydrate (0.011 part by mass) and 600 parts by mass of methyl isobutyl ketone. And stirred to obtain a mixture. 12.7 parts by mass of ethyl vinyl ether (protecting agent) was added to the mixture obtained above while stirring. Then, while stirring at 25 ° C., the reaction mixture after 30 minutes was sampled twice to prepare standard samples 2-71 to 2-72 (1 for each).
Mass part).

Thereafter, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature and sampled twice from the reaction mixture after 30 minutes (+60 minutes), to obtain standard samples 2-73 to 2-74 (1 part by mass each). Then, while stirring at the same temperature, ethyl vinyl ether 2.
9 parts by mass was added, and the mixture was stirred at the same temperature, sampled twice from the reaction mixture after 30 minutes (+90 minutes), and the standard sample 2-
75 to 2-76 (1 part by mass for each). Then, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature and sampled twice from the reaction mixture after 30 minutes (+120 minutes), to obtain standard samples 2-77 to 2-7.
8 (1 part by mass each). Then, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature and sampled twice from the reaction mixture after 30 minutes (+150 minutes), to obtain standard samples 2-79 to 2-80. (Each 1 part by mass). Then, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature and sampled twice from the reaction mixture 80 minutes later (+230 minutes later) to obtain standard samples 2-81 to 2-82. (Each 1 part by mass).
Then, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature for 30 minutes (+26
After 0 minutes), the reaction mixture was sampled twice to obtain standard samples 2-83 to 2-84 (each 1 part by mass). Then, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature and sampled twice from the reaction mixture after 30 minutes (+290 minutes), to obtain a standard sample 2-85-2.
-86 (1 part by mass for each). Then, 2.9 parts by mass of ethyl vinyl ether was added with stirring at the same temperature, and the mixture was stirred at the same temperature and sampled twice from the reaction mixture after 30 minutes (+320 minutes), to obtain standard samples 2-71 to 2-88. (1 each
Mass part). Table 13 shows the relationship between each standard sample and the take-out time.

(Lot 2-11) Lot 2-1 except that the same starting polymer compound used in Lot 2-2 was used instead of the same starting polymer compound used in Lot 2-1.
Operate in the same manner as for 0 to prepare standard samples 2-89 to 2-10
6 (1 part by mass each). Table 14 shows the relationship between each standard sample and the extraction time.

[Determination of Protection Rate of Standard Sample by NMR Method] A polymer compound was obtained from the standard sample obtained above in the same manner as in Example 1, and its ¹ H-NMR spectrum was measured to obtain p- It was confirmed that a polymer compound in which a protecting group (ethoxyethyl group) was introduced into the hydroxyl group of the vinylphenol monomer unit was formed, and the hydroxyl group protection rate of the polymer compound (n _i1 , i is 1 to 1 106 is shown).
The results are shown in Tables 4 to 14.

[Measurement of Near Infrared Absorption Spectrum of Standard Sample] In the same manner as in Example 1, the near infrared absorption spectrum (r _{1 to} r ₁₀₆ ) of the standard sample was obtained.

[Preparation of Multiple Regression Calibration Curve] The wave number range used for calculation of the near infrared absorption spectrum (r _{1 to} r ₁₀₆ ) of the standard sample obtained above was set to 7500 to 6099 cm ⁻¹ , and the measured spectrum was interpolated. Then, the calculated wave number interval is set to about 1 cm ^-1 (the number of data points is 1454 points), the primary differential processing and the smoothing processing are performed as the preprocessing, and the matrix [R] is obtained according to the procedure 2 to the procedure 3, and the matrix [U ],
The number of floors (M) was calculated. M was 7. ¹ H-N above
The protection rate of the standard sample obtained from the MR spectrum (n _i1 ,
The matrix [N] was obtained based on the above equation (1-1) using i = 1 to 106). In _{addition, n ik (i = 1~106,} k = 2~
7) was set to 1. When [N ′] was obtained according to the procedure 4 and the error (e) was obtained according to the procedure 5, the value was 0.877. FIG. 6 shows the relationship between the protection rate (n _i1 , i = 1 to 106) and the element (n ^′ _i1 ) of the matrix [N ′] at this time. Also,
Tables 4 to 14 show n ^′ _i1 .

Then, according to procedure 7, the matrix [T] showing the multiple regression calibration curve was obtained. The spectrum (r
_The error (e) was determined in the same manner as above by changing the wave number range and pretreatment used for the calculation of _{1 to} r ₁₀₆ ), but all exceeded 0.877.

[0084]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protection rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-1 2-1 0 hours After 0 0.19 1 2 2 2 2-1 After 0 hours 0 0.21 2 2 -3 2 1 After 1 hour 23.2 23.09 3 2 4 2-1 After 1 hour 23.2 23.00 4 2-5 2-1 After 2 hours 23.9 23.94 5 2-6 2-1 2 hours later 23.9 23.74 6 2-7 2-1 +1 hour later 26.3 25.81 7 2-8 2-1 +1 hour later 26.3 25.84 8 ━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

[0085]

[Table 5] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i Sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-9 2-20 hours After 0.0 -1.06 9 2-10 2-20 0 hours After 0.0 -1.06 10 2-11 2-2 After 1 hour 25.4 28.80 11 2-12 2-2 After 1 hour 25.4 28.82 12 2-13 2-2 2 hours 25.3 25.47 13 2-14 2-2 2 hours later 25.3 25.32 14 2-15 2-2 + 1 hour later 29.2 28.51 15 2-16 2-2 + 1 hour later 29.2 28.29 16 2-17 2-2 + 2 hours later 28.6 28.73 17 2-18 2-2 + 2 hours later 28.6 28.38 18 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0086]

[Table 6] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-19 2-30 hours After 0.0 0.25 19 2-20 2-3 After 0 hours 0.0 0.18 20 2-21 2-3 After 1 hour 16.7 16.76 21 2-22 2-3 After 1 hour 16.7 16.59 22 2-23 2-3 After 2 hours 17.2 18.74 23 2-24 2-3 After 2 hours 17.2 18.46 24 2-25 25 After 3 hours 16.9 16.45 25 2-26 2-3 After 3 hours 16.9 16.42 26 ━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

[0087]

[Table 7] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2- 27 2-40 0 hours After 0 -0.54 27 2-28 2-4 0 hours After 0 -0.74 28 2-29 2-4 1 hour after 24.3 24.72 29 2-30 2-4 1 hour after 24.3 24.48 30 2-31 2-4 2 hours 25.9 25.74 31 2-32 2-4 2 hours later 25.9 25.47 32 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0088]

[Table 8] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protection rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-33 2-50 hours After 0.0 0.40 33 2-34 2-5 After 0 hours 0.0 0.46 34 2-35 2-5 After 1 hour 27.6 27.49 35 2-36 2-5 After 1 hour 27.6 27.27 36 2-37 2-5 After 2 hours 28.7 28.27 37 2-38 2-5 2 hours later 28.7 28.09 38 2-39 2-5 + 1 hour later 29.8 29.73 39 2-40 2-5 + 1 hour later 29.8 29.40 40 ━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

[0089]

[Table 9] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protection rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-41 2-60 0 hours After 0.0 -0.09 41 2-42 2-6 0 hours After 0.0 -0.52 42 2-43 2-6 After 1 hour 17.4 17.81 43 2-44 2-6 After 1 hour 17.4 17.32 44 2-45 2-6 2 hours After 17.9 18.15 45 2-46 2-6 After 2 hours 17.9 17.61 46 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0090]

[Table 10] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-47 2-7 0 hours After 0.0 0.21 47 2-48 2-7 After 0 hours 0.0 -0.13 48 2-49 2-7 After 1 hour 27.6 28.02 49 2-50 2-7 After 1 hour 27.6 27.52 50 2-51 2-7 After 2 hours 27.8 28.74 51 2-52 2-7 2 hours later 27.8 28.38 52 2-53 2-7 + 1 hour later 31.5 32.14 53 2-54 2-7 + 1 hour later 31.5 31.67 54 2-55 2-7 + 2 hours later 32.1 32.96 55 2-56 2-7 + 2 hours later 32.1 32.62 56 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0091]

[Table 11] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-57 2-8 1 hour 23.3 22.63 57 2-58 2-8 1 hour later 23.3 22.02 58 2-59 2-8 2 hours later 23.4 22.96 59 2-60 2-8 2 hours later 23.4 22.40 60 2-61 2-8 + 1 hour later 25.3 25.96 61 2-62 2-8 + 1 hour later 25.3 25.34 62 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0092]

[Table 12] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2- 63 2-9 1 hour After 24.8 25.32 63 2-64 2-9 After 1 hour 24.8 24.85 64 2-65 2-9 After 2 hours 25.6 25.75 65 2-66 2-9 After 2 hours 25.6 25.14 66 2-67 2-9 After 3 hours 26.4 25.96 67 2-68 2-9 3 hours later 26.4 25.31 68 2-69 2-9 + 1 hour later 29.5 30.11 69 2-70 2-9 + 1 hour later 29.5 29.52 70 ━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

[0093]

[Table 13] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2- 71 2-10 30 minutes After 3.0 3.93 71 2-72 2-10 After 30 minutes 3.0 3.26 72 2-73 2-10 After 60 minutes 8.1 8.47 73 2-74 2-10 After 60 minutes 8.1 7.89 74 2-75 2-10 After 90 minutes 14.4 14.62 75 2-76 2-10 After 90 minutes 14.4 14.04 76 2-77 2-10 After 120 minutes 18.0 17.93 77 2-78 2-10 After 120 minutes 18.0 17.36 78 2-79 2-10 After 150 minutes 23.3 22.98 79 2-80 2-10 150 minutes later 23.3 22.64 80 2-81 2-10 230 minutes later 29.1 29.81 81 2-82 2-10 230 minutes later 29.1 29.48 82 2-83 2-10 260 minutes later 31.4 32.74 83 2- 84 2-10 After 260 minutes 31.4 32.51 84 2-85 2-10 After 290 minutes 36.3 36.22 85 2-86 2-10 After 290 minutes 36.3 35.80 86 2-87 2-10 320 minutes later 41.8 41.12 87 2-88 2-10 320 minutes later 41.8 40.67 88 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━

[0094]

[Table 14] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Standard lot Extraction time Protection rate Protected rate calculation value i Sample n _i1 (%) _n'i1 (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2- 89 2-11 30 minutes After 3.5 3.95 89 2-90 2-11 After 30 minutes 3.5 3.46 90 2-91 2-11 After 60 minutes 7.6 8.20 91 2-92 2-11 After 60 minutes 7.6 7.61 92 2-93 2-11 After 90 minutes 14.1 14.78 93 2-94 2-11 90 minutes later 14.1 14.26 94 2-95 2-11 120 minutes later 18.4 18.51 95 2-96 2-1 1 120 minutes later 18.4 18.20 96 2-97 2-11 150 minutes later 23.5 24.59 97 2-98 2-11 150 minutes later 23.5 24.01 98 2-99 2-11 230 minutes later 32.0 31.94 99 2-100 2-11 230 minutes later 32.0 31.59 100 2-101 2-11 260 minutes later 35.4 35.74 101 2- 102 2-11 260 minutes later 35.4 35.21 102 2-103 2-11 290 minutes later 40.1 38.02 103 2-104 2-11 290 minutes later 40.1 37.66 104 2 105 2-11 320 minutes later 44.7 44.53 105 2-106 2-11 320 minutes later 44.7 44.51 106 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━

[Preparation of Measurement Sample] Copolymer of p-Vinylphenol and Cyclohexyl Acrylate [Raw material polymer compound, weight average molecular weight is 13000, p-vinylphenol monomer unit (first structural unit) is 90% by mole fraction, cyclohexyl acrylate monomer unit (other structural units) is 10% by mole fraction) 100 parts by mass, paratoluenesulfonic acid monohydrate (catalyst, 0.011 parts by mass) and 600 parts by mass of methyl isobutyl ketone (solvent) were mixed and stirred to obtain a mixture. With stirring the mixture obtained above, 13.0 parts by mass of ethyl vinyl ether (protecting agent) was added dropwise over 30 minutes. Then, while stirring at 25 ° C., the reaction mixture was sampled from the reaction mixture after 1 hour and 2 hours from the completion of the dropping, and measured sample 2-107.
2 to 108 (each 1 part by mass).

Thereafter, the mixture was stirred at the same temperature for about 1 hour, ethyl vinyl ether (2.2 parts by mass) was further added while stirring at the same temperature, and 1 hour after the addition (+1 hour after addition) while stirring at the same temperature. Is indicated twice.) Was sampled twice from the reaction mixture, and one of them was used as a measurement sample 2-109 (1 part by mass). Table 15 shows the take-out time of each measurement sample.

[Determination of protection rate by NMR method] The above standard
Measurement sample 2-107 as in sample
~ 2-109 ¹H-NMR spectrum is measured and protected
I asked for the rate. The results are shown in Table 15.

[Determination of Protection Rate Using Multiple Regression Calibration Curve] Near infrared absorption spectra (x) of Samples 2-107 to 2-109 were determined in the same manner as in the above standard sample, and the number of spectra (x) was calculated. Range 7500-6099
Using the data of cm ^-1 (data point number: 1454 points), the primary differentiation process and the smoothing process were performed as pre-processing to obtain the protection rate (y). The results are shown in Table 15. The time required to measure the near-infrared absorption spectrum is 30
It was within seconds. When the spectrum (x) was subjected to pretreatment to obtain the protection rate, an ordinary personal computer was used, and the protection rate could be obtained almost instantly.

[0099]

[Table 15] ━━━━━━━━━━━━━━━━━━━━━━━━ Measurement take-out time Protection rate (%) Protection rate (%) Sample NMR method y ━━━━━━━━━━━━━━━━━━━━━━━━ 2-107 1 hour later 12.6 12.8 2-108 2 hours later 13.7 13.2 2-109 +1 hour later 17.2 16.9 ━━━━━━━━━━━━━━━━━━━━━━━━

As shown in Table 15, the calculated value (y) of the protection rate calculated from the near infrared absorption spectrum (x) of the sample using the multiple regression calibration curve is the quantitative value of the protection rate determined by the NMR method. Match.

[Brief description of drawings]

FIG. 1 is a diagram showing a relationship between [Procedure 1] to [Procedure 7].

FIG. 2 is a diagram showing a near-infrared absorption spectrum of a standard sample 1-14 prepared in Example 1, where the horizontal axis represents the wave number (W
ave Number, cm ^-1 , 12000-5300
cm ⁻¹ ) and the vertical axis represents the absorbance (arbitrary unit).

FIG. 3 is a diagram showing a near-infrared absorption spectrum of a standard sample 1-15 prepared in Example 1, in which the horizontal axis represents the wave number (W
ave Number, cm ^-1 , 12000-5300
cm ⁻¹ ) and the vertical axis represents the absorbance (arbitrary unit).

FIG. 4 is a diagram showing a near-infrared absorption spectrum of a standard sample 1-19 prepared in Example 1, in which the horizontal axis represents the wave number (W
ave Number, cm ^-1 , 12000-5300
cm ⁻¹ ) and the vertical axis represents the absorbance (arbitrary unit).

FIG. 5 is a diagram showing the relationship between the quantitative value of the protection rate by the NMR method (horizontal axis) of the standard sample obtained in Example 1 and the calculated value of the protection rate (vertical axis) calculated from the multiple regression calibration curve. is there.

FIG. 6 is a diagram showing the relationship between the quantitative value of the protection rate by the NMR method (horizontal axis) of the standard sample obtained in Example 2 and the calculated value of the protection rate (vertical axis) calculated from the multiple regression calibration curve. is there.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Norifumi Yamaguchi             3-1,98-1 Kasugade, Konohana-ku, Osaka             Tomo Chemical Co., Ltd. F term (reference) 2G059 AA05 BB08 EE01 EE10 EE12                       FF04 FF08 HH01 HH06 MM01                       MM03 MM12 MM17

Claims (9)

[Claims] 1. A near-infrared absorption spectrum of a plurality of standard samples is subjected to principal component regression analysis from the near-infrared absorption spectra of a measurement sample containing a polymer compound consisting of the following first structural unit and second structural unit. A method for quantifying the protection rate of hydroxyl groups of a polymer compound, which comprises calculating the protection rate of hydroxyl groups of the polymer compound using the obtained multiple regression calibration curve. First structural unit: structural unit having a structure having a hydroxyl group Second structural unit: structural unit having a structure in which a protective group is introduced into the hydroxyl group in the first structural unit 2. The quantification method according to claim 1, wherein the hydroxyl group is a phenolic hydroxyl group. 3. The first structural unit is of formula (I) The quantification method according to claim 2, which is a structural unit represented by: 4. The quantification method according to claim 1, wherein the protecting group is an alkoxyalkyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyl group or an alkoxycarbonyl group. 5. A method for producing a polymer compound comprising the following first structural unit and second structural unit by reacting a starting polymer compound comprising the following first structural unit with a protecting agent: Protecting the hydroxyl groups of the polymer compounds contained in the reaction mixture by using the multiple regression calibration curve obtained by subjecting the near-infrared absorption spectra of the reaction mixture during the reaction to the main component regression of the near-infrared absorption spectra of multiple standard samples. Calculate the rate,
A method for producing a polymer compound, which comprises stopping the reaction based on the obtained protection rate. First structural unit: structural unit having a structure having a hydroxyl group Second structural unit: structural unit having a structure in which a protective group is introduced into the hydroxyl group in the first structural unit 6. A method for producing a polymer compound comprising the following first structural unit and second structural unit by removing a protecting group from a starting polymer compound comprising the following second structural unit: From the near-infrared absorption spectrum of the reaction mixture during the reaction, using the multiple regression calibration curve obtained by principal component regression analysis of the near-infrared absorption spectra of multiple standard samples, the hydroxyl group of the polymer compound contained in the reaction mixture A method for producing a polymer compound, which comprises calculating a protection rate and stopping the reaction based on the obtained protection rate. First structural unit: structural unit having a structure having a hydroxyl group Second structural unit: structural unit having a structure in which a protective group is introduced into the hydroxyl group in the first structural unit 7. The method according to claim 5, wherein the hydroxyl group is a phenolic hydroxyl group. 8. The method according to claim 7, wherein the first structural unit is a structural unit represented by the formula (I). 9. The method according to claim 5, wherein the protective group is an alkoxyalkyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyl group or an alkoxycarbonyl group.